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by Kate Fisher B.E, Photovoltaics and Solar Energy, 2004
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that electroless metal layers. however. heavily diffused surfaces. backside buried contact (IBBC) solar cells. are not adherent on pit contact IBBC solar cells. It is shown. adhesive Cu deposits on planar <100> surfaces is developed in this thesis.and p. pit contact IBBC solar cells were not able to be fabricated during the course of this work but it is reasonable to expect that the modiﬁed plating sequence developed in this work will result in the metal layers being adhesive on these cells.Abstract This thesis focuses on improving the adhesion of electroless metal layers plated to pit contacts in interdigitated. an electrolessly plated Cu layer will cause the underlying Ni layer to peel away from the substrate. Fully plated. the contact grooves are replaced with lines of pits which are interconnected by the plated metal. In an electrolessly plated. in the absence of a silicide at the Ni/Si interface. It is shown that this process leads to the formation of a Ni silicide on both n. An electroless metallization sequence that results in thick. pit contact IBBC cell.type. The cause of this adhesion problem is investigated by examining the adhesive properties of each of the metal layers in the electroless metallization sequence on planar test structures. plated by the standard IBBC plating sequence. . It is also found that the Ni silicidation process itself intermittently causes the unreacted Ni to spontaneously peel away from the substrate. This investigation reveals that Pd activation of heavily P diffused Si impedes Ni silicide growth and that.
Dedication ..to a world with fewer problems.... .
My understanding of solar cells and skills in the laboratory have beneﬁted from this employment opportunity and your guidance as a boss and a supervisor has helped very much in realising this thesis. Dr Jeffery Cotter for providing me with the opportunity to carry out this research. I would like to acknowledge the love.vii Acknowledgements Firstly. I would not have been able to undertake it without the ﬁnancial support of employment in the same ﬁeld (and physical space) as my research. . Thanks also for the historical information. Thanks to Florence Chen and Jeff also on this front. as usual. I would also like to thank Malcom Abbott for his ﬁne proof reading skills and ability to utilise them to great effect at very short notice. Thanks also goes to Dr Tom Puzzer for training and enlightening discussions on electron microscopy and willingness to divulge an astonishing wealth of information about analytical measurement techniques. thanks. Parents. Special thanks to Stuart Wenham for being so forthcoming with processing tips and tricks for buried contact solar cells. support and not inconsiderable cooking skills of my partner Sami. I would like to thank my supervisor. Particular thanks also to Jenny Norman and other staff at the electron microscope unit for helping me wrestle with the Cambridge (it was a beast but I’m still sad to see it go).
List of Abbreviations AED BGD BPSG BSF BSG CMOS c-Si CZ DSBC EB EDS EDTA EWT FZ IBBC IC PCD PERL PGD PSG Autocatalytic Electroless Deposition Boron Groove Diffusion Boro-Phospho-Silicate Glass Back Surface Field Boro-Silicate Glass Complementary Metal Oxide Semiconductor Crystalline silicon Czochralski Double-Sided Buried Contact Electron Beam Energy Dispersive Spectroscopy Ethyl-Diamine-Tetraacetic Acid Emitter Wrap Through Float zoned Interdigitated Backside Buried Contact Intergrated Circuit Photoconductance Decay Passivated Rear Locally Diffused Phosphorus Groove Diffusion Phospho-Silicate Glass .
ix RIE RTP SEI SEM SPM SSBC TCA UNSW Voc Reactive Ion Etching Rapid Thermal Processing Secondary Electron Image Scanning Electron Microscope Sulfuric Peroxide Mixture Single-Sided Buried Contact Trichloroethane University of New South Wales Open Circuit Voltage .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . .2. . . . . . . . . . . . . . . . . . . . . . . .5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ni Silicidation . . . . . . .3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Electroless Metallization of Silicon Solar Cells . . . . . . . . . . . . . . . .1 2. . . . . . . Autocatalytic Electroless Depositions . . 1 1 4 4 6 7 7 8 9 11 14 15 18 20 22 24 27 Literature Review: Electroless Metallization 2. . . . . Thesis Outline . . . . . . . .4. . . . . . . .2 2. . . . . . . . . . . . . Silicidation of AEDs . . . . . . . . . . . Buried AED Contacts . . . . . . . .1 1. . . . .2. . . . . . . . . . . . . . . . . . Electroless Plating .3 1. . . . 2. . . . . . . . 2.2 Planar AED Contacts . . . . . . . . . . 2. . . . .1 2.4 2 Motivation . . . . . . . . 2. . . . . . . . . . . . .4. . . . . . . . . . . . . . . . Thesis Statement . . . . . . . . . . . . . . . . . . . . . . . .2 Introduction . .Contents Chapter 1 Introduction 1. . . . . . .2 Silicidation of Pure Ni Deposits . . . . . . .2 1. . . . . . . .3 Palladium Immersion Activation . . . . . . . . . . . . . . . . . Thesis Contributions . . . . . . . . . . . . . . . 2.1 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 2. . .
. . . . . . .3. . . Ni Sintered Pits . . . 3. . . . . 4. . . . . . .3 4. . . . . . . . . . . . . . . . . . . . .2. . . . . . . . .1 3. . .3. . . . . . . . . . . . . 28 28 28 28 31 34 35 36 39 40 41 43 43 44 44 45 47 53 53 55 56 57 57 59 63 64 66 Experimental Method . . . . . . . . . . . . . . . 4. . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . .2.2 4. . . . . . . . . . . . . . . . . . . . . . 4. . . . . .1 4. . . . . . . . .4 Effect of Surface Activation . . . . . Preliminary Experiments . . . . . . . . . . . . . . . . . . . . . .1 4. . . . . .2 Introduction . . . . . . . . . . . . . . . . . . .4 Electroless Plating . . . .3 4. . . . . . . . . . . . . . . . . . . . . . . . . . .1 3. . . . . . . .2 4. . . . . . . . . Experimental Results and Discussion 4. . . . . . . . . . .1 4. .3 3. . . . . . . Effect of Ni Plating Temperature . . . . . . . . . . . . . .xi 3 Research Methodology 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4. . . . . . . . . . . . . . . .2. . . . . . . . . . . .4. . . . . . . . . . . . . . . . . . .3. . . . . . . . .3. . . . . . . .3 4. . . . Ni Sintering . . . . . . . Background Information . . . . . .2 3. . . . . Pd Activated Pits . . . . . . . . . . . . . . . . . . . . .2. . . . . . . . Effect of Pd Sintering . . 4. . Metal Adhesion Problems of Pit Contacts . . . . . . . . . . . . . . . . . . . . .4 4 Summary . Plating Buried Contact Solar Cells .4 Ni Plated Pits . . . . . .4. . . . Metallization of Pit Contacts . . . . . . . . . 3. . .4. . . . . . . . . . . . . . . . . . . . . . . . . . . Pd Cleaning . . . . . . .3 Buried Contact Solar Cell Structures . . .2 4. .2 3. . . . . . . . . . . . . . . . . .2 Introduction . . . . . . . . . . Pits and Grooves: a Photoconductance Comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . Conclusions . . .4 Ni Silicidation . . . . . . . .3. . . . . . .3. . . . . . . . . . . . Unreacted Ni . . . . . .1 4. . . . . . . . . .2. . . . . . . . Ni Cleaning . . . . . . .1 3. . .3 Pits and Grooves: a Structural Comparison . . . . . . 3. . . .
. . .5. . . . . . . . . . . . .4. . . . . . . . . 67 68 69 70 72 73 75 Cu Plated Layers . . . .1 4. . . . . . . . . . . . . . . . . . Conclusion and Future Work Appendix A SEM and EDS 79 Bibliography 81 . . . . . . . With Ni Silicide . . . . . . . 4. . . . . . . . . 4. . . . . . . . . . . . . . . . . . . .6 5 Summary . . . . . . .5 Conclusions .5. . . . . . . . . . . . . . . . . . . . . . . .3 Without Ni Silicide . . . . . . . . . . . . . . . . . . . . . . .5. . . . . . .xii 4. . . . . . . . . . . . . . . . . . . .5 4. . .2 4. . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . The results are shown in Figure 4. . . . . . . . . . . . . . . . All substrates are (100). 35 59 60 35 25 30 34 23 19 17 . . . . . 3. . .1 Summary of Ni silicide phase transitions and sheet resistivity results from various authors.1 3. . . . . . . . . . . . . .2 Phenomena observed for AEDs of Ni plated to (100) substrates and sintered at various temperatures. . . . . . . .3 Summary of processing parameters of various c-Si solar cells with planar. . . 4. . . . . . . . . . . . . . . . . . . . 2. . . Deposition 2 refers to 30-40 nm of NiP plated to Pd activated. . . . . . . . . . . . .1 4. . 2. . . . . . . . . Deposition 1 refers to 30-40 nm of NiP plated on EBNi seed layers on n-type substrates . .16. . . . . . . . . photolithographically deﬁned. Silicidation test structure types. . . . . . . . . Bath constituents of an ammonia-based. .3 . c-Si . n-type substrates  and Deposition 3 refers to 800-3000 nm of NiP plated directly onto p-type 1-10Ωcm substrates . . . . . electrolessly plated contacts. Summary of the experiment.2 3. . . electrolessly plated contacts. . . . . . . . . . . . proprietary electroless Ni plating solution from Transene .4 Summary of processing parameters of various c-Si solar cells with buried. . . . . . . . . . . . . . .3 IBBC solar cells processing sequence prior to metallization. . . . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . .List of Tables Table 2. . . . . .4 Bath constituents of a proprietary electroless Cu plating solution from Enthone . . . . . 3. . . . .2 Summary of results from Section 4. . . . . . . . . . . . . . . . .
. .4. . . . . . .xiv 4. .6 Pd sintering on boron diffused test structures. . . . . 4. . . . . . . . . . . .4 4. . . . . . Measurements were taken before the plating sequence (ie: this is the sheet resistivity of the phosphorus diffusion). . 72 . . Ni plating and sintering parameters for three SSBC PGD test structures with photolithographically deﬁned contacts. Sample 2 was sintered at 300◦ C and Sample 3 was sintered at 400◦ C. . . . . . . . . . . . . . . . . . . . . . . .1 and 4.4. . . . . . . . and after the unreacted Ni had been removed (ie: this is the resistivity of the phosphorus diffusion and the Ni silicide in parallel). . .3 Sheet resistivity variation with Ni sintering temperature. . . 71 61 64 68 Sheet resistivity measurements of the various layers formed on photolithographically deﬁned contacts. . . .7 . . Summary of results from Sections 4. . . 4. . .5 4. . .3 . . . . . . . . . . . . . . . . . .
. . . . . hypophosphite bath at 90-95◦ C onto (a) n-type surfaces and (b) p-type surfaces (after ). . . . The substrates here are 4 Ω. . . . . . . . tends to agglomerate. . . . . . . . . . . p-type (after ). . 2. . . . . formed at higher temperatures. . AED of Ni plated from an alkaline. . . . . .List of Figures Figure 2. . . The surface concentration of the n-type substrates was 4-8 x 1015 /cm3 and for p-type substrates. . . . . . . . . . . In general. . . . . . .1 2. .cm. . . . . . . . . . . . . . . . . . . . The activation solution is NH4 F-based and the Pd deposit was sintered for 30 minutes at 200◦ C prior to the Ni plate. P+ denotes a boron diffused surface and N+ denotes a phosphorus diffused surface both with surface concentrations >1020 /cm3 . . . . . . 2. . . . . . . . . . . x1 < x2 < x3 and the Si rich phase. with and without Pd activation. . .3 Adhesion of an AED of Ni plated to variously doped substrates. . activated with various Pd solutions. . . . . The graphs show adhesion of a 2 minute.4 A summary of the most commonly reported phases of Ni silicide and their temperatures of formation. . All substrates are (111). . Adhesion of an AED of Ni plated to variously doped substrates. . The Pd layer was sintered for 30 minutes at 200◦ C prior to the Ni plate.2 Schematic of the electroless plating sequence for IBBC solar cells. . . . . 1-2 x 1016 /cm3 . . . . . . . . . . . . Adhesion as a function of (a) surface concentration and dopant type for various Pd activation solutions and (b) Pd solution type for various Ni plating times and temperatures. . . 17 12 12 8 . . . .
.5 Schematic of various electroless plated contacts. .6 Temperature proﬁle of furnace used for Ni silicide formation . . . . . front surface. rear surface. . . . Photolithographically deﬁned contacts with a planar homogeneous emitter. . . . with phosphorus and passivated with SiO2 . . . . diffused to < 10 Ω/sq. . . . . . diffused with 100 Ω/sq. . . . diffused to < 5 Ω/sq with phosphorus. . . . A scribed contact with a selective emitter is shown in d). . . . . . . . (c) sintered at 400◦ C without the use of an elephant. . .4 Schemaitic of an elephant. . 3) laser scribed grooves. . . Section a) shows the Ni plate intact. . . 3.xvi 2. . . . b). . . . (d) sintered at 400◦ C without the use of an elephant and with the furnace N2 turned down. . . . . . 3. . Three sections of a boron diffused sample that has been Ni plated. phosphorus emitter and passivated with SiO2 . . . . . . . . . The effects of O2 on electroless plated Ni when heated. . . . . . . . . . front surface. .3 3. . . and a buried selective emitter are shown in a). respectively. . . . . .1 Schematic of a SSBC solar cell showing 1) random pyramid textured. . . . The samples have been Ni plated and (a) no sintered. . . diffused to < 5 Ω/sq with phosphorus. . (b) sintered at 200◦ C without the use of an elephant. . . 2) saw damage etched.5 3. b) shows the Ni plate removed with RCA2 and c) shows the Ni plate removed with SPM. . . . . . . . . . boron emitter and passivated with SiO2 . a planar selective emitter. . . . 40 38 38 29 37 29 22 . . . Ni and Cu plating in both rear grids. . with boron and 5) Pd. . . . . . . . Dotted lines indicate diffused Si. . . and c). . diffused to 100 Ω/sq. . . light grey areas indicate the dielectric and dark grey areas indicate the plated metal. . . 3. 4) laser scribed grooves. 4) Ni and Cu plating in the front surface grid and 5) Ni and Cu plated over the entire rear surface. . 3) random pyramid textured rear surface with an aluminium back surface ﬁeld. . . . . 2) laser scribed grooves. . . . . . diffused with 100 Ω/sq. . . . 3.2 Schematic of a IBBC solar cell showing 1) random pyramid textured.
. . 4. . . . . . .5 SEM micrograph of poorly adhesive electroless Ni and Cu plated on the pits of several ﬁngers of an IBBC cell. The pits were scribed with a laser wavelength of 1064 nm and hence end up being 20 μm across. . . .xvii 3. . . 4. . . . . . . . . . . . 4. . . . . . Saturation current contribution from the diffused regions as a function of contact type. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The border with rounded corners in the plane view corresponds to the Si overhang and there is no oxide overhang in the cross section because the oxide was thinner to begin with and hence got etched back to the edges. . . . . . . . . . . . . . . 4. . . . . . The pits are spaced 50 μm apart and hence the adjacent pits are out of the frame of this image. . . . . . . . .1 Ni and Cu plated 50 μm deep groove on an IBBC solar cell showing the void at the centre of the trench and 50 μm of overplating. . . . .6 a) A busbar on a pit IBBC cell showing how the Cu plating has fallen out of the pits and b) a close-up of the top left hand corner of the same busbar. . . . . . . . . 4. . . . . 4. . . . . . . . . . .6 b). . . . The left side of b) has been swabbed with a cotton bud soaked in IPA and the right side has been SPM cleaned and then swabbed with a cotton bud soaked in IPA.7 A boron diffused wafer a) after Pd activation and b) the same wafer after cleaning. . . . . Pit 2 and Pit 3 in Figure 4. . . . . . . . . . 51 51 50 49 48 46 48 46 41 . .7 A ﬁnger on a pit IBBC cell showing the Cu plate detaching from the Ni plate in the pit. . . . . 4. . . . . . . The numbers refer to the pit to the right of the number. . . . . . . . .3 4. . . . . . . . . . . The ﬁrst and third ﬁngers are phosphorus diffused and the second and fourth ﬁngers are boron diffused. . . . . . .4 Injection-level dependence lifetime curves of the various contact types.8 SEIs and EDS maps of the pits labeled Pit 1. .2 SEM micrograph of (a) the plane view and b) the cross section of etched pits. . . . . . . . . . . . . . . . . Note the oxide overhang in the plane view and the Si overhang in the cross section. . . . . . . . . . . . .
. . . . . . .19 The three different test structures with three different surface treatments prior to electroless Ni plating at 90-92◦ C for 4 minutes. The samples had different Pd treatments prior to electroless Ni plating at 80◦ C for 4 minutes. . . . .17 Boron groove diffused samples that have been Pd activated and the Pd sintered for a) 10 minutes at 250◦ C and b) 40 minutes at 200◦ C. . 4. . . . the unreacted Ni was removed in SPM. . . .9 An example of badly deglazed a) phosphorus and b) a boron diffused pits. . . . . . . The samples were sintered for 10 minutes at the temperatures indicated and the unreacted Ni removed in a 50% SPM. . . . . plated with electroless Ni. . . . . . Pd activated a) phosphorus and b) boron diffused pit. . . . . . . . . . .14 A well deglazed.18 Silicide formation on an a) IBBC phosphorus and b) boron test structure that was Pd activated and the Pd sintered at 250◦ C for 20 minutes. . 4. . . . . . . . . . . . . . . . . . . . . 4.15 The Pd activated a) phosphorus and b) boron diffused pits after sintering and RCA2 to remove the unreacted Ni. . . . .16 P-type substrates with SSBC PGD of 3 Ω/sq. . . . . . . 4. 56 4. . . . . . . . . . . . . . . . . . . . . . . . . . 4. .12 An a) phosphorus diffused and b) a boron diffused pit that has been Ni plated at 90-95◦ C after sintering at 350◦ C and removal of the excess Ni in RCA2 solution. . .13 Ni plated onto the ﬁeld oxide. . . . . with Pd activation and electroless Ni plating at 80◦ C. . . . . . . . . Finally. . . .10 An example of well deglazed a) phosphorus and b) a boron diffused pits. . . plated with electroless Ni. . . . . 4. . 4. . .11 Pit contacts that have a) had no plating at all and b) been Ni plated at 90-95◦ C and the Ni removed in a standard RCA2 etch (no sintering). . . . . . . . . . 4. . . . . . across the whole surface. . . . . 66 65 64 62 58 58 58 56 54 54 . . . . . The samples were sintered at 350◦ C for 5 minutes and the unreacted Ni removed in a SPM. . . . . . . . . . . . . . . . 4. . . . .xviii 4. The bottom left pit is plated with Cu but all other pits and the areas between them were determined to be Ni by EDS mapping. . . . . . . . . . Both samples then underwent SPM cleaning prior to Ni plating and at 300◦ C. . . . . .
. . . . . a) the SEI image of the mapped area. . . . . . . . . . . . . . . . . . . .24 Plan view of two SSBC PGD test structures that were photolithographically patterned and metallized. . . . .22 Cu plated layers on phosphorus diffused IBBC test structures that were ﬁrst plated with Ni at a) 80◦ C and b) 90◦ C. . . . . . . . .1 X-ray spectrum generated on a Ni plated pit at low magniﬁcation (black spectrum) and at high magniﬁcation (grey spectrum). . . A. . . . . . . . . . . . .2. . 4. . . . . . . . . . . . After the initial Ni deposition. . . b) the Si signal. . . . . . . . .20 IBBC phosphorus diffused test structures with three different surface treatments prior to electroless Ni plating at 90-92◦ C for 4 minutes. . . . . . . . . . . . 80 80 80 71 70 69 67 66 . . . . .21 A photograph of Ni ﬂaking off a test structure after sintering at 300◦ C for 7 minutes. a) the SEI image of the mapped area. . . The samples were sintered at 300◦ C for 5 minutes and the unreacted Ni removed in a SPM. 4. . . . 4. . A. both samples were sintered at 300◦ C for 10 minutes and the unreacted Ni was a) left on and b) removed in an SPM before further processing. . . . . . . . . . . c) the Ni signal and d) the phosphorus signal. . . .23 Cross sectional schematic of the photolithographically deﬁned pattern used in Section 4. . . . . . . . . A. . . . . . . . . . .xix 4. . . . . . . . . . . . c) the Ni signal and d) the phosphorus signal. . . 4. . . . . . . .2 X-ray maps of a Ni plated pit. . . . . . .3 X-ray maps of a pit where the Ni has been sintered and the unreacted Ni removed with RCA2. . . . . . b) the Si signal.5. . . . . . . . . . . . . . .
1 Motivation Metallization is an important area of solar cell research because energy is extracted from a solar cell through its metal contacts. low resistivity contacts but they are expensive to manufacture and are not suitable for use in high through-put production lines. Ideally. This thesis looks in detail at another metallization technique: electroless plating.Chapter 1 Introduction 1. Ti-Pd-Ag contacts are utilised in high efﬁciency laboratory devices such as PERL cells . Screen printed contacts are applied to the cell surface by forcing a metal paste through an emulsion screen using a squeegee. In order to electrolessly plate metal to a solar cell. enable high through-put and incur minimal manufacturing costs. The majority of photovoltaic devices in the market today use screen printed contacts. Many different metallization schemes are employed in photovoltaic devices. Vacuum evaporated. they will be easy to manufacture. has low contact and series resistance and incurs low shading losses. Vacuum evaporation yields high purity. This is because the high throughput capabilities of this technique make it highly suitable for use in commercial production lines. the Si must be exposed in the contact areas and . A good metallization scheme is one that provides low recombination. Screen printed contacts incur substantial shading losses and have high bulk resistivity . The metal contacts must also adhere well to the surface of the cell. Many cells also use vacuum evaporated or sputtered Al contacts (see  for example).
2 masked everywhere else. The grooves are scribed through the surface dielectric. One example of photovoltaic devices that utilise electroless metallization schemes are the buried contact solar cells. This ensures low contact resistance between the metal and the semiconductor . which has the advantage of providing low contact resistance . Low temperature processing reduces the thermal budget and the probability of contamination.the single sided buried contact . is that there are more steps in the processing sequence. Buried contacts (BCs) are photovoltaic devices in which contact is made to the cell by applying metal into grooves scribed into the wafer surface either mechanically or with a laser. The maximum processing temperature is ∼ 400◦ C whereas screen printed contacts are typically ﬁred at ∼ 800◦ C. Shading losses from screen printed contacts are also high because the minimum line width is ∼ 120 μm . There are three buried contact solar cell structures . An electroless deposition of Ni is then plated to the contact areas and sintered in a furnace to form a low resistance Ni silicide at the contact interface. compared to screen printing. The main disadvantage of electroless metallization. will initiate on the Ni surface. which comprises the bulk of the metal contact. Screen printed pastes incorporate solvents and frits  that result in printed contacts having much higher series resistance than plated contacts. Burying the metal contact areas vertically inside the substrate reduces the opaque area on the front surface. Electroless metallization schemes utilise Ni silicide at the contact interface. Another layer of Ni is then plated to the ﬁrst layer as a strike. Cu is used as the bulk material because of it’s low bulk resistivity. or deﬁned by laser or mechanical scribing . It also means that the doping level in the emitter can be as low as 100 Ω/sq. which results in good utilisation of the solar spectrum . which acts as a mask for a heavy diffusion in the contact areas. . which reduces shading losses. A thin layer of Ag is often plated over the Cu to better facilitate soldering. Electroless plated contacts can be much narrower because they are deﬁned photolithographically . Electrolessly plated contacts have many advantages compared to screen printed contacts. . This ensures that the subsequent Cu plate.
formed during this heavy diffusion. It was found. simply by changing the laser scribing code. lightly diffused phosphorus front surface ﬁeld and both heavy boron and phosphorus contact diffusions in an interdigitated pattern on the rear surface . which has been shown to provide excellent surface passivation . the new code would create a line of pits. for example). which would need to be electrically connected by the metallization scheme. IBBCs also incur no shading losses because the contacts are on the rear surface and efﬁciencies approaching 20% on 180 μm thick. The base contact is realised with a heavily. N-type. because the capture-cross section of holes is much lower than that of electrons (see . 1 Ωcm FZ wafers have been demonstrated with this cell structure . The base contact is realised with a thin Al alloyed region over the entire rear surface. Instead of creating a groove in the wafer surface. the double sided buried contact (DSBC) and the interdigitated backside buried contact (IBBC). IBBCs are not affected by asymmetric-SRH recombination in the way that p-type DSBCs are. The IBBC solar cell comprises an n-type base. . light phosphorus diffusion on the rear surface . buried contact grid scribed through the ﬂoating junction. boron misﬁt dislocations. This diffusion acts as a ﬂoating junction. . This results in voltage limitations for thin cells with long diffusion lengths. boron diffused. Cells with this type of grid design are called pit contact IBBC solar cells. The DSBC seeks to overcome this limitation by replacing the Al rear contact with a well-passivated. however that diffusion induced. lightly diffused boron emitter. severely limit the performance of these cells because they cause asymmetric Schottky-Read-Hall (asymmetric-SRH) recombination in the bulk . Point contact IBBC structures could potentially be made for no extra cost.3 (SSBC). because the rear surface recombination velocity high . A common way to increase the performance of high efﬁciency. Realisation of pit contact IBBC solar cells by electroless metallization is the subject of this thesis. SSBCs comprise a phosphorus emitter on a p-type substrate with emitter contact grooves scribed through the passivating dielectric . c-Si solar cells is to reduce the surface area of the heavily diffused contact regions by using points of contact instead of lines or whole surfaces of contact .
3. every time the process is run. from a layer of electrolessly plated Ni. To determine the main parameters affecting electroless Ni plating of heavily phosphorus and boron diffused silicon. 4. Ni silicide formation and Cu plating of Ni. electroless metallization scheme and their interdependency were identiﬁed experimentally. Developing a reliable process generally requires the effects of the ﬁrst and second order parameters of the process to be known and controllable. To develop a process that allows a silicide to form. 1. simultaneously on heavily phosphorus and heavily boron diffused Si. pit contact. four intermediate goals were identiﬁed: 1. To achieve the main goal of producing an electrically operational. To develop a reliable method for simultaneously plating electroless Ni to heavily phosphorus and heavily boron diffused Si. A reliable process is one in which the same outcome is achieved for the same processing parameters. The main contributions of this work can be summarised as follows: . It is necessary to understand the main parameters of each one in order to gain control over the process as a whole. To develop a method of electrolessly plating thick layers (> 50 μm) of Cu to a heavily diffused Si/silicide/Ni region.2 Thesis Statement The aim of this thesis is to develop a reliable electroless metallization scheme that en- ables maximal current extraction from pit contact. The most important ones are Ni plating of Si. IBBC solar cell. 2. The electroless metallization scheme of the IBBC solar cell is comprised of a sequence of distinct processes.4 1. IBBC solar cells. the main parameters of each of the processes of the IBBC.3 Thesis Contributions During the course of this thesis.
5 • Bath activation greatly affects the initiation of autocatalytic electroless depositions of both Ni and Cu. • An electroless plating sequence was developed that allowed adhesive layers of thick Cu to be plated to planar. but allowed for a macroscopic view of the silicidation process. IBBC solar cell was not achieved during the course of this work. It was shown that Ni silicide formation could be examined on planar dummy wafers by plating and sintering a Ni layer and then removing the unreacted Ni in a selective wet chemical etch. Inclusion of the groove diffusion dummy wafers into the metallization processing sequence. • Incomplete silicidation can cause the unreacted Ni to peel away from the underlying silicide. (100) test structures. . that such a device is unlikely to ever be realised by electroless metallization. This allowed for a macroscopic view of the silicidation process and proved to be a much more efﬁcient way of examining problems with the metallization process than manufacturing batches of cells. This thesis shows. In addition to these ﬁndings. The main objective of producing an operational. • Plating thick Cu layers to Ni plated layers on planar Si substrates causes adhesion failure at the Ni/Si interface unless the Ni layer is bonded to the substrate by silicidation. not only greatly improved the platability of the samples. • Ni plating bath temperature greatly affects silicide formation. several processing techniques were developed during this work to allow the parameters of each of the processes to be examined. however. pit contact. • Pd activation of heavily phosphorus diffused (100) Si impedes silicide formation for furnace sintering temperatures up to 450o C and sintering times of less than 10 minutes.
Section 4. Chapter 4 describes and discusses the experiments carried out during the course of this work.4.2 and the electroless plating.2. Chapter 2 presents a review of published work per- taining to the electroless metallization of Si solar cells.3 describes an experiment that shows that Pd activation of heavily diffused boron pits is necessary to avoid excessive Si migration during Ni sintering. Ni sintering and metal cleaning techniques used in this work are presented in Section 3.4 Thesis Outline This thesis has three main chapters.4 presents the results of experiments that show how Pd activation inhibits Ni silicide formation on heavily phosphorus diffused surfaces and how unreacted Ni may be one potential source of poor adhesion in the IBBC electroless metallization scheme. Section 4. Chapter 3 describes the experimental method used in this thesis. Section 4.6 1.3 and a discussion of the application of these is presented in Section 2.3. The main ﬁndings of this work are summarised in Chapter 5 and options for future work are discussed. The potential beniﬁts of pit contact IBBC solar cells and the problems encountered in their metallization is presented in Section 4.5 presents evidence that a lack of Ni silicide at the Ni/Si interface is another potential source of adhesion failure and shows that proper silicidation in conjunction with the removal of the unreacted Ni after silicidation imporves the adhesion of subsequent Cu plated layers. A review of the contact structures used in UNSW buried contact solar cells is presented in Section 3. Different types of electroless plating are reviewed in Section 2. . the silicidation of Ni is reviewed in Section 2.2.
1 Introduction This chapter presents a review of the literature that is relevant to the experimental work carried out in this thesis.1. Activation of the contact areas with Pd (b). Plating mechanisms and the . is employed to better facilitate Ni plating and improve contact adhesion. A thin layer of Ni is then plated to the contact areas (c) and sintered to form a silicide at the Ni/Si interface (d). The literature pertaining to electroless metallization of IBBC has been reviewed and grouped into three topic areas. A thick layer of Cu is then plated to the second Ni layer (f). The ﬁrst is electroless plating. All oxide is removed from the contact areas leaving bare Si exposed (a). Cu is used as a low resistance current carrier because it’s bulk resistivity is ∼ 4 times lower than that of Ni and it is much cheaper than lower resistivity metals such as Ag or Au. The electroless plating sequence utilised in IBBC solar cells is broken down into it’s constituent parts and the literature pertaining to each part is reviewed in order to gain an understanding of the mechanisms affecting each of the layers.Chapter 2 Literature Review: Electroless Metallization 2. Formation of the Ni silicide reduces the contact resistance between the metal and the Si and anchors the metal to the cell. A schematic of the steps in the IBBC solar cell metallization sequence is shown in Figure 2. The main aim of this thesis is to improve the adhesion of electrolessly plated layers to pit contact IBBCs. A second layer of Ni is then plated over the top of the ﬁrst layer (e) to better facilitate Cu plating.
There are two types of electroless plating that are utilised in solar cell metallization and they proceed by different mechanisms. properties of each of the metal deposits are presented in Section 2.2.1: Schematic of the electroless plating sequence for IBBC solar cells.2 Electroless Plating Electroless plating refers to the deposition of metal onto a substrate from an aqueous medium without the use of an external bias potential to drive the reaction. In Section 2. These are mostly concerned with vacuum deposits of Ni sintered by rapid thermal processing (RTP).3 an understanding of the mechanisms involved in Ni silicidation is sought from the proliﬁc amount of literature available pertaining to silicidation in CMOS devices. 2. The second topic to be reviewed is Ni silicide formation. After Ni has been plated to an IBBC solar cell it is sintered to form Ni silicide at the contact interface. The purpose of this section is to highlight the beneﬁts of electroless metallization in comparison to other metallization schemes and to identify some of the known problems associated with the process. The third topic is to be reviewed is the electroless metallization of c-Si solar cells in general and buried contacts in particular.2. The effect of plating bath parameters on the properties of electroless Ni and Cu depositions is presented in Section 2. The plating .8 a) Si b) Pd c) Ni d) NiSi e) Ni f) Cu Figure 2. The few publications that have considered the silicidation of AEDs of Ni by furnace processing are then reviewed to gain some insight into the actual silicidation process occurring on IBBC devices. The ﬁrst is referred to as immersion plating or immersion activation.2. Section 2.1 discusses how Pd activation can affect the adhesive properties of subsequent metal deposits.2.
which plate a much greater rates. . Pd has a much greater propensity to plate out of solution than Ni.1 is more likely to proceed than the reverse reaction . allows the non-conductive substrate to be metallized.2. The mechanisms behind autocatalytic electroless deposition and the properties of Ni and Cu AED baths and deposits are discussed in Section 2. It has been shown that p-type Si has a lower electroless Ni nucleation density than n-type Si . because it increases the Ni nucleation density. The Pd layer. the substrate is ﬁrst sensitized with Sn then .2. Autocatalytic electroless depositions. Pd immersion is therefore useful for activating heavily boron diffused Si. This is due to the electronegativity of p-type Si being greater than that of n-type which causes the plating rate to be much lower on p-type surfaces than on n-type .1 Palladium Immersion Activation Pd is often used as a seed layer for subsequent AEDs on non-catalytic substrates or substrates where nucleation is minimal. The higher the concentration of p-type dopants. positive redox potential which means that the forward reaction of Equation 2. which has a negative redox potential. (AEDs).  and  for example). can ﬁrst be activated with a thin layer of Pd (see: .1. for example. the worse this problem becomes.83 V (2. where the transfer of electrons is limited. For example. The chemical equation for the reduction of Pd ions to Pd metal is given by Equation 2.9 rate from an immersion plating bath is typically low and the layers are generally used as a seed layer for a subsequent autocatalytic deposit. Pd ions will be reduced to Pd metal on any substrate from which they can gain electrons.1. are used to plate the bulk of the conductor. non-conductive materials.2. Pd 2+ + 2e − Pd E o = 0.1) To plate Pd to insulating or otherwise non-catalytic substrates (such as printed circuit boards). The mechanisms behind immersion plating and the type of immersion plating utilised in IBBC solar cells are discussed in Section 2. Pd has a relatively high. that would otherwise not be able to be plated by an autocatalytic process. which acts as a catalyst for many AED solutions. 2.2.
There have been reports of Pd activation of Si in HF-free solutions but without discussion of the plating mechanism . however. A comprehensive study of the effects of HF-based Pd activation on the adhesion of subsequent AED layers has been carried out by Karmalkar et. Defects on or near the surface (such as diffusions) have also been found to cause inhomogeneous Si dissolution during Pd activation . Several authors found that Pd activation of Si is not possible without the inclusion of HF in the solution . When the substrate is Si. sintered to form a Pd silicide and swabbed with iso-propyl alcohol to remove any residue.2) When Si is immersed in a mixture of Pd and HF.. . a galvanic reaction proceeds where anodic dissolution of the substrate (Equation 2. . This means that too little NH4 F or NH4 OH for a given volume of PdCl2 will result in a high level of chlorine complexes and the subsequent AED may be non adherent.10 activated with Pd and the Sn removed at the end in a acceleration step (for examples see: . Si + 6F − SiF6 2− E o = 1. a much simpler process is possible due to fact that Si dissolves in HF according to Equation 2. . Too much of these additives .24 V (2. prior to AEDs of Pd and Ni. . Cu and Pd are all able to be immersion plated to p-type.1) by transferring electrons through the substrate . One study found that for c-Si and a-Si surfaces (of unspeciﬁed dopant concentrations) the HF concentration did not affect the size and distribution of the Pd aggregates plated from a chloride-based solution but the number of dissolution etch pits increased with increasing HF concentration . Various substrates were activated with Pd from various bath types. . al.2 . The Pd-diamine complex was found to improve adhesion compared to the Pd-chlorine complex while the Pd-tetramine complex inhibits subsequent plating .  and ).2) enables cathodic reduction of the metal ions from the solution (Equation 2. (100) Si from sulfate solutions (with HF) and that the HF concentration greatly affects the nucleation rate for the case of Cu .  . They found that the adhesion of subsequent AEDs on Pd activated samples is not governed by the HF concentration but by the Pd complex. It has been shown that Au.
For this reason. This suggest that the nucleation density of the Ni plate on heavily diffused boron surfaces is increased by Pd activation . decreasing the minority carrier lifetime and increasing junction leakage .3 shows that diamine-based activation does not signiﬁcantly improve the adhesion of AEDs of Ni on n-type.3 show a summary of the results of Karmalkar et al.4.3 of this work. . especially when heavily doped. and if located near a junction. 2. Ni and Cu contacts can both be plated by AED onto Si. that are relevant to the adhesion of plated layers activated by Pd immersion.11 will convert all the diamine complexes to tetramine complexes which can result in the AED not plating as fast or at all. Figure 2.2 a) shows a comparison of activation baths on various surfaces. For this reason.2 b) also shows that increasing the thickness of the Ni AED reduces the adhesion which is probably due to increased stress in the deposits .4. Ni and Ni silicide is used as an interlayer between Cu contacts and Si substrates in Si solar cells.2 b) shows that lowering the AED plating temperature also reduces adhesion.2. . This is a potential cause of poor adhesion in the pit contact IBBCs and is investigated in Section 4. Pd and each other. Diamine-based baths improve the adhesion of AEDs of Ni in comparison to HF based ones for p-type surfaces but don’t affect the adhesion on heavily doped n-type surfaces. a thinner Ni layer was used in the experiments of Chapter 4 than in the standard IBBC plating sequence.2 Autocatalytic Electroless Depositions Cu is used in integrated circuits due to it’s low resistivity and superior resistance to electromigration. This may be related to the results of Section 4. Figures 2. Figure 2.2 and 2. can act as a trap. Figure 2. Figure 2. The Pd bath used in the standard IBBC plating sequence is Bath F from . (111) surfaces in comparison to no activation but does improve adhesion on p-type surfaces.a phenomenon that is demonstrated experimentally in Section 4. Interestingly.2. Pd immersion plating was found to improve the adhesion of AEDs of Ni more than AEDs of Pd and adhesion of both metals was reduced if the immersion layer was not sintered . It is a fast diffuser in Si however.3 which shows that silicide formation does not occur on unactivated samples plated at low temperatures.
p-type (after ). hypophosphite bath at 90-95◦ C onto (a) n-type surfaces and (b) p-type surfaces (after ). 1-2 x 1016 /cm3 . The substrates here are 4 Ω. The graphs show adhesion of a 2 minute. P+ denotes a boron diffused surface and N+ denotes a phosphorus diffused surface both with surface concentrations >1020 /cm3 . . The surface concentration of the n-type substrates was 4-8 x 1015 /cm3 and for p-type substrates. with and without Pd activation. The activation solution is NH4 F-based and the Pd deposit was sintered for 30 minutes at 200◦ C prior to the Ni plate. a) b) Figure 2.12 a) b) Figure 2.2: Adhesion of an AED of Ni plated to variously doped substrates. The Pd layer was sintered for 30 minutes at 200◦ C prior to the Ni plate. All substrates are (111). activated with various Pd solutions. Adhesion as a function of (a) surface concentration and dopant type for various Pd activation solutions and (b) Pd solution type for various Ni plating times and temperatures.3: Adhesion of an AED of Ni plated to variously doped substrates.cm. AED of Ni plated from an alkaline.
cm to 120 μΩ.13 The mechanism that drives AED is much the same as that of immersion plating except that the reduction of the metal ions is enabled via an oxidation reaction within the solution. Netherlands published in ).3) (2. to be electrochemically controlled . Copper plating baths typically contain complexants. AEDs of Ni do not result in a pure Ni deposit on the catalytic surface but in an alloy with a composition that is dependent on the reducing agent.H2 O plating baths can be employed .3% as the pH was varied . at a catalytic surface. does affect the decomposition of formaldehyde. These often allow the bath to be operated at higher pH values. It has been shown that Ni cannot be used as a catalyst for the oxidation of formaldehyde  so the deposition of Cu on Ni must proceed by another mechanism in these baths. but here the discussion is mostly conﬁned to alkaline/Ni/NaH2 PO2 . however. The plating rate is therefore kinetically limited by the oxidation step.cm as the phosphorus content varies from 0 . Ni/NaH2 PO2 .H2 O) as the reducing agent. rather than by dissolution of the substrate.4) Formaldehyde is employed as the reducing agent in autocatalytic electroless Cu plating . Both acid and alkali. . It has been shown that the P content of Ni AEDs varies from 4.7% to 3. and variation of diffusion mechanisms (increasing the metal ion concentration or agitating. The use of sodium hypophosphite (NaH2 PO2 . for example) will not change it. The reduction of Cu2+ has been shown to be diffusion limited and the oxidation of formaldehyde.12 wt% (data from Enthone. stabilizers and exaltants which stop the Cu ions precipitating in the bulk solution and change the initiation conditions.H2 O baths. Generically. The catalytic nature of the substrate. The resistivity of the a NiP alloy increases from 10 μΩ. the process is represented by simultaneous anodic oxidation and cathodic reduction : Reducing Agent Metal z+ + ze − Reducing Agent z+ + ze − Metal (2. A pure copper-formaldehyde-water bath needs to be operated below a pH of 6 . . yields deposits of NiP alloys while deposits of NiB alloys can be obtained by using sodium borohydride (NaBH4 ) as the reducing agent .
The phosphorus content of the deposit is also increased by increasing the plating temperature . 2. It was found that NiP ﬁlms plated from an alkaline. such as the potential for shunting and the extra processing steps. Cu can be plated directly to Si but it can not be heated to obtain good adhesion because of it’s high diffusion coefﬁcient in Si and potential . Differences in the Ni plating rates on n. Ni plating solutions containing EDTA were not able to plate the heavily boron diffused grooves but that EDTA-free solutions  and maintaining high pH values and temperatures  could overcome the problem. This was also found to be the case in this work. As with AEDs of Cu. In acid baths the same trend is observed but it is much more pronounced and the P content is generally higher than in alkali baths . One study found that this difference increased with increasing illumination but equal plating rates could be obtained by the addition of 6g/L of ethyl-diamine-tetra-acetic acid (EDTA) into the plating solution . The ﬁrst is to reduce the contact resistance at the metal/semiconductor interface. Ni-hypophosphate bath at 90◦ C onto n-type. however.3 Ni Silicidation Ni silicide is used in IBBC solar cells for two reasons. .and p-type surfaces have also been reported .14 from 8 to 12 . . but not the NiCl2 concentration . The contact regions of a BC cell. The catalytic effect of the substrate also plays an important role in the AED of Ni. 3-5 Ω. are so heavily doped that the beneﬁt of forming a Ni silicide. however. EDTA concentrations greater than this suppressed plating altogether on both substrate types.cm samples were thicker on (100) surfaces than on (111) surfaces . The plating rate is known to be directly proportional to the bath temperature and increasing the pH will also increase the plating rate . thick Cu layer. AEDs of Ni are also kinetically limited by the oxidation step and therefore dependent on the hypophosphite concentration . in comparison to a Ni/Si interface on heavily doped Si. The second reason for forming a silicide on IBBC solar cells is to promote adhesion of the subsequent. alkalibased. it was found that proprietary. often does not outweigh the draw backs. When plating DSBC solar cells.
1. . . Si rich. 1.5 μm of NiSi will form .4. . for example). as shown in Figure 2. . If the temperature of the system is raised high enough the epitaxial. . . .  and . . For every micron of Ni2 Si reacted. for example) at pressures of less than 10−6 Torr and the Ni silicide formed by rapid thermal processing (RTP). ). .3.  and . in order to better understand and control Ni silicidation in IBBC solar cells. It is well established that for thin ﬁlms of pure Ni on Si substrates. . for example). . which improves the adhesion of the existing Ni layer and of subsequent plated layers. a review of literature published on the theory and experimental results of Ni silicidation is presented. . the ﬁrst phase that forms is the Ni rich Ni2 Si phase which is stable up to 250-300◦ C (for examples see: . If the supply of Ni stops (if it is all consumed for instance or if the silicide layer becomes sufﬁciently thick for the diffusion of Ni to the Si interface to become negligible) and energy is still supplied to the system then the phase of the silicide will change depending on the temperature.  and . As the temperature is raised and all the Ni is consumed the excess Ni in the Ni rich phase then diffuses to the Si interface forming NiSi in the temperature range 300-700◦ C (for examples see . ).1 Silicidation of Pure Ni Deposits Ni silicide is used extensively in CMOS devices because of its low sheet resistivity. .4.4 μm of Ni2 Si will form . for example) or e-beam evaporation (see . . Ni is known to be the dominant mobile species in a Ni-Si system such that the growth of silicide is limited by the diffusivity of metal atoms through the silicide layer(s) to the Si interface (see . forms stable silicides when heated. . For every micron of Ni consumed. and . Ni. NiSi2 phase begins to form (for examples see . low silicon consumption and ability to form narrow line widths without compromising resistance (see . .15 to form traps. . on the other hand. A summary of this is shown in Figure 2. . . Silicide gates and interconnects in IC devices are generally formed by sputtering (see . The NiSi2 phase is generally uneven in thickness and characterised by agglomeration of Si at the surface . In this section. ). 2.
the sheet resistivity on As implanted wafers was 30 Ω/sq. A 30 nm Ni ﬁlm can be completely converted to the low resistivity NiSi phase in the temperature range 400-700◦ C. This factor has been taken into account in . As shown in Table 2. n-type substrates but when they were BF2 + implanted.16 Table 2. Similar sheet resistivities as those given in table 2.cm. which is formed below 300◦ C. which has sheet resistivity in the range 1.1 for Ni silicide ﬁlms were also observed in this work (see Sections 4. is less conductive than the NiSi phase. as a thin layer of Ni on a Si substrate is heated from room temperature to 900◦ C. For sintering temperatures between 350◦ C and 550◦ C the sheet resistivity was the same on both polarity samples (7 Ω/sq) but for sintering temperatures between 260◦ C and 330◦ C. The silicide ﬁlms were prepared by Ni sputtering and RTP.NiSi2 without the formation of NiSi on samples with boron implanted through the Ni ﬁlms has also been reported . It shows that. The NiSi phase was found to form at a lower temperature on the B implanted samples because Ni diffusion through the Ni2 Si layer is faster with a higher density of grain boundaries.7 Ω/sq. Sintering at temperatures higher than this causes the sheet resistivity to increase.4.1 and 4. (100).5. Stabilisation of the Ni2 Si phase and transition from Ni2 Si . the affect of temperature on Ni silicide phase transformation has been well characterised in the literature. which is usually attributed to agglomeration of the ﬁlm during the NiSi to NiSi2 phase transformation. Hence. the order of the phase transformations was different. dopant density at the substrate surface has also been found to affect the phase transitions during Ni silicide growth. while on B implanted wafers it was 70 Ω/sq. the resistivity of the ﬁlm changes as the phase of the silicide changes. Another study observed the usual Ni2 Si-NiSi-NiSi2 phase transitions on 3-8 Ω. While not as well characterised. (100) substrates .1 presents a summary of sheet resistance measurements of Ni silicide layers found in the literature. One study found a signiﬁcant difference in the sheet resistivity of Ni silicide ﬁlms prepared on As and B ion implanted.1. The Ni2 Si phase. with the NiSi2 phase being found to form at much lower temperatures .8 . This was attributed to a difference in the grain size which was found to be smaller on B implanted samples. the correlation between sheet resistivity and silicide phase that exists for undiffused samples is not the same for diffused samples.2).
10 20 .30 1 .700 600 .700 500 .3.4: A summary of the most commonly reported phases of Ni silicide and their temperatures of formation. Type N P N P P P N P P P Doping (Ω.900 700 . . .30 Thickness of Ni (nm) 30 30 30 27 30 30 30 27 30 30 ∗ units are in μΩ.1: Summary of Ni silicide phase transitions and sheet resistivity results from various authors.17 Figure 2. .5 7 1.300 350 .700 400 . All substrates are (100).6 2.8 3. .10 110 1.5 2.13∗ 3.5 Source           Table 2. .30 1 .450 400 .5 .) 6 .10 20 . formed at higher temperatures.8 .5 .30 3-8 20 . .600 450 .30 3-8 20 .3. .5 30 . In general.cm) 3-8 20 .800 800 700 . c-Si . .800 Phase Ni2 Si Ni2 Si NiSi NiSi NiSi NiSi NiSi + NiSi2 NiSi2 NiSi2 - Sheet Resistivity (Ω/sq. .cm Sintering Temperature (◦ C) 200 . tends to agglomerate. . x1 < x2 < x3 and the Si rich phase.
The growth rate. These ﬁndings were conﬁrmed by another study which found that the growth rates of both Ni2 Si and NiSi on 1-10 Ω. Crystal orientation of the substrate has been found to affect the silicidation growth rate. however. This means that when transferring the process from test structures to cells. was found to form on the EB-Ni and Pd-activated samples at temperatures of 300◦ C and 400◦ C. a phenomenon also observed elsewhere  and in this thesis (see Section 4.18 the experiments of this work. Their ﬁndings are summarised in Table 2.325◦ C.3. respectively . (100) and (111) substrates . This was attributed. The Ni2 Si phase (only) was formed on both substrate orientations.cm.2 shows that Pd activation tends to inhibit Ni silicide formation. In this thesis silicide formation and the adhesion of subsequent AEDs is observed on planar.2 Silicidation of AEDs It has been reported that there are considerable differences in the phase transformations at low temperatures for AEDs of Ni compared to vacuum depositions. to . 1-10 Ω. n-type substrates sintered in the temperature range 300◦ C-370◦ C was nearly double on (100) substrates compared to (111) substrates .cm Si plated in alkaline.cm. sintered at various temperatures for 1 hour . The ﬁlms were sintered in a vacuum in the temperature range 200◦ C . NiCl2 -NaH2 PO2 baths at 95◦ C. Table 2. Epitaxial NiSi2 .2. NiSO4 -NaH2 PO2 based baths at 70◦ C on n-type. (100) samples. however was found to be signiﬁcantly higher on (100) substrates than on (111) substrates. Another reports a similar study of AEDs of Ni on p-type. One study compared Ni silicide formation from 160 nm thick. One author studied the Ni-silicide phase transformations of 30-40 nm AEDs from acidic. sintered at various temperatures for 1 hour . vacuum evaporated Ni ﬁlms on 2-10 Ω. usually reported to form above 600◦ C. In a pit contact IBBC solar cell. The substrates were activated with either a seed layer of electron beam evaporated Ni (EB-Ni) or SnCl2 sensitized Pd. the contacts are inverted pyramids with (111) facets.4). by the authors. longer sintering times may need to be employed in order to form the same thickness of silicide. 2. as expected at this temperature. (100) substrates.
19 Sintering Temperature As Deposited 200◦ C 300◦ C 400◦ C 500-700◦ C >800◦ C Deposition 1 3 nm amorphous layer at AED-Ni interface 20 nm unreacted NiP. phosphorus diffusion. It is possible that the presence of the Ni3 P layer is due to the presence of the amorphous interlayer (assumed to be oxide). n-type substrates  and Deposition 3 refers to 800-3000 nm of NiP plated directly onto p-type 1-10Ωcm substrates . the presence of a Ni3 P layer at the surface. p-type wafer with a 20-30 Ω/sq. Ni2 B or NiBSi were not detected on samples where boron was implanted through a pure Ni ﬁlm  and the formation of a Ni3 P layer was not observed for Deposition 3 in Table 2. at temperatures as low as 275◦ C. epi-NiSi2 NiSi only NiSi and poly-NiSi2 Deposition 3 Ni3 Si2 major NiSi traces Ni3 Si2 major NiSi minor NiSi major Ni3 Si2 minor NiSi2 major NiSi minor Ni3 Si2 traces Table 2. are probably also contributing . formed from AEDs of Ni varying in thickness from 800-3000 nm . The formation of the NiSi phase. and the dopant level at the surface. Sintering was carried out in a furnace in air ambient.2. the preceding discussion indicates that the nature of the Ni layer (pure Ni or NiP). Deposition 2 refers to 30-40 nm of NiP plated to Pd activated. For example. This silicide layer was formed on the (111) facets of a textured. which has not been previously reported. no reaction at interface 10 nm NiSi 20 nm. 15 nm epi-NiSi2 10 nm Ni3 P 10 nm NiSi 20 nm epi-NiSi2 NiSi only NiSi and poly-NiSi2 Deposition 2 1. (100). reducing the metal concentration at the interface and hence inhibiting the metal rich phase formation. has also been reported for AEDs of Ni . Although the authors attribute the low temperature formation of the NiSi phase to the orientation of the plated surfaces. Others. a Ni3 Si2 phase.2: Phenomena observed for AEDs of Ni plated to (100) substrates and sintered at various temperatures. Deposition 1 refers to 30-40 nm of NiP plated on EB-Ni seed layers on n-type substrates . however. have not found impurity containing phases.5 nm amorphous layer at AED-Ni interface Ni3 P at surface. Instead.
photosensitive layer onto the wafer surface and the patterning of this layer by exposure to light through a detachable mask. Heavy doping levels. 2. The contact pattern is formed in the dielectric layer by immersing the wafer in such an etching solution. The contact pattern is then developed in the photosensitive layer which is resistant to certain etches that will dissolve the underlying dielectric. silicidation of AEDs of Ni is not as well characterised or as predictable as the silicidation of vacuum deposits of Ni. Oxides or nitrides or a combination of the two are generally employed in c-Si solar cells as anti-reﬂection coatings and for surface passivation and they can also be used as plating masks. In order to plate metals in a contact pattern on the cell surfaces.4 Electroless Metallization of Silicon Solar Cells The electroless metallization techniques described in Sections 2. substrate orientation and doping level. For this reason it is generally used in conjunction with vacuum evaporated metals for high efﬁciency. laboratory devices (see . Patterning a dielectric layer by photolithography involves the deposition of a temporary.3 have been applied in various combinations to various types of c-Si solar cells. It is also clear that. impurities within the plated layer. Clearly. Photolithography can achieve ﬁne line widths (on the order of a few microns) but it is slow.2 and 2. These dielectrics can be patterned in various ways. The photosensitive layer is then removed. for example). dopant type and Pd activation all play an important role in determining the characteristics of the resultant Ni silicide.20 factors in this case. the most common of which are photolithography and scribing. the wafer must ﬁrst be masked and the contact pattern deﬁned in the mask such that only the contact areas plate. variable impurity levels in the Ni plate. Contact openings can also be made through the ﬁeld dielectric by laser or mechanical . Pd activation and plating of (111) surfaces formed in (100) wafers are all features of IBBC solar cells and should be taken into account during silicide formation. costly and involves many processing steps.
1 and 2. are used which results in adequate contact resistance to the wide.) in localised regions under the metal contacts. that minimises both series resistance and shading losses. Laser and mechanically scribed contacts are generally ∼ 30 μm wide and ∼ 50 μm deep .4. high resistivity printed pastes but substantial emitter recombination losses . Planar contacts with either homogeneous or selective emitters (Figure 2. The ideal emitter sheet resistivity. ablated Si from the contact areas . because a second diffusion is required. . To make ohmic contact between a metal and a semiconductor. to remove loose. If contact resistance was not an issue. Scribing processes not only remove the dielectric mask in the contact areas but usually some of the underlying Si as well. this usually corresponds to sheet resistances lower than about 20 Ω/sq.5 a) and b).21 scribing. Doping an emitter to this level.2. In screen printed solar cells. better cell performance could be achieved by going to higher emitter sheet resistivities and thinner.5 c) and d). Such a cell can be realised by the use of a selective emitter.4.) over most of the cell surface but heavy doping (less than 20 Ω/sq. less resistive ﬁngers. There are various studies reported in the literature which utilise the different techniques of fabricating electroless contacts in silicon solar cells. . respectively) can be made using photolithography. Figure 2. For conventional furnace diffusions. depends on the geometry and resistivity of the ﬁngers .60 Ω/sq. would result in substantial recombination losses in the emitter. A discussion of the electrical and adhesion properties of such contacts are presented in Sections 2. a minimum surface concentration of 1019 dopant atoms/cm2 is required at the interface . Three dimensional or buried contacts can be made using either photolithography in conjunction with etching or laser or mechanical scribing (Figure 2. respectively). and usually require an additional diffusion step.5 shows the various types of solar cell contacts that can be made using photolithographically deﬁned or scribed contact openings. emitter sheet resistances of ∼ 40 . A selective emitter has light emitter doping (typically ∼ 100 Ω/sq. Emitters with buried contacts can be homogeneous but are usually selective. Laser scribed contacts require alkaline etching prior to further processing. to minimise contact resistance.
2.1 Planar AED Contacts Several devices with electroless contacts plated to photolithographically deﬁned open- ings in the ﬁeld dielectric have been reported in the literature. and c). exhibited IV characteristics consistent with a high concentration of recombination centres in the diode due to excessive Ni diffusion.5: Schematic of various electroless plated contacts.3. A scribed contact with a selective emitter is shown in d). Cells with furnace sintered. light grey areas indicate the dielectric and dark grey areas indicate the plated metal. however. a planar selective emitter. b). respectively. One study compared cells with Ni plated contacts sintered by two different methods to cells of the same structure with vacuum evaporated Ti-Pd-Ag contacts . A summary of the processing used in these is presented in Table 2. phosphorus diffused emitters and all ADEs of Ni are in fact Ni-P.22 a) b) c) d) Figure 2. Ni plated contacts.4. and a buried selective emitter are shown in a). The Ni sintering time at 270◦ C was varied and it was found that cells sintered for 40 minutes exhibited only . Another study compared cells with plated contacts to the same cells with Al sputtered contacts and found the IV behaviour of both cell types to be the same . All the cells are p-type with homogeneous. Dotted lines indicate diffused Si. The Ni plated cells that were sintered by rapid thermal processing (RTP) had only marginally poorer IV characteristics than the Ti-Pd-Ag ones. It found that the adhesion and series resistance of the Ni plated contacts was poorer than the Ti-Pd-Ag contacts. Photolithographically deﬁned contacts with a planar homogeneous emitter.
) 30 30 30 20-30 14 Pd Sinter Time (min) Pd Sinter Temp (◦ C) Ni Sinter Ambient N2 RTP Vacuum Air N2 Silicide Various Various NiSi NiSi N/A Other Metal None None Cu + Sn † Solder None Source      Table 2. electrolessly plated contacts.Cell Type Pd Type PdCl-HCl PdCl-HCl PdCl3 -HF 30 30 30 350 350 290 15 RTP 20 5 15 400 RTP 270 260 240-400 Ni Sinter Time (min) Ni Sinter Temp (◦ C) Plated Surface Planar 111 Planar 111 Planar 100 Textured 111 Planar 111 † Electrolytic Cu was then solder dipped Sheet Resistivity (Ω/sq.3: Summary of processing parameters of various c-Si solar cells with planar. 23 . photolithographically deﬁned.
8 and Cell No.4 lists the parameters of various types of electrolessly plated solar cells with buried contacts and selective emitters. One of the drawbacks of electroless plating of buried contacts is that the metals plate faster at the corners of the grooves than inside them resulting in the grooves being closed off before they can be ﬁlled .4. The mechanically scribed and etched contacts were 40 μm wide. with and without Pd activation. 5) all result in a thin layer if metal on the walls of the grooves and overplating at the groove . This does not appear to be a problem for the small.3 illustrates that it is possible to plate adhesive AEDs of Ni to planar (as opposed to buried) surfaces and form a silicide at the Ni/Si interface on both (100) and (111) surfaces. . 1 which were able to be completely ﬁlled with an adhesive AED of Ni . The laser scribed grooves of Cell No. square shaped grooves of Cell No.3  all exhibit similar IV characteristics. 2.24 a small degradation in Voc while Voc was reduced by 20% in cells that were sintered for 60 minutes. The grooves on Cell No. Table 2. 60 μm deep and diamond shaped . Mechanically scribed grooves plated with electrolytic Ag (Cell No. Cell No. Cell No. This suggests that the non-optimal IV curves observed by Lue for the furnace sintered cells are the result of to high an sintering temperature (see Table 2.3). 9 are the same depth as the mechanically scribed ones but only half as wide . Only one of the authors reported the adhesion of Ni to be a problem on planar surfaces who observed that the Ni layer would ﬂake off at a thickness of 1 μm . 2 is an example of a buried contact made by mechanical scribing and the rest are all laser scribed buried contacts. 2) and small laser scribed grooves plated with electroless Cu (Cell No. The cells that were sintered for 20 minutes  and the cells with RTP Ni contacts  and the textured cells in Table 2. 4 are of a similar shape but the dimensions are approximately 25 μm x 25 μm . The RIEed contacts had a 5 μm x 5 μm square cross section . 1 is an example of a buried contact produced by photolithography and reactive ion etching (RIE). 4) or with non-optimised electrolytic Cu (Cell No.2 Buried AED Contacts Table 2.
1 μm) + Cu (5 μm)† AED Ni (2 μm) + electrolytic Cu† AED Ni + Cu (50μm) AED Ni + Cu (50μm) AED Ni + Cu (50μm) AED Ni + Cu (50μm) Heavy Chemical roughening PdCl2 -HCl-HF-NH4 OH PdCl2 -HCl-HF-NH4 OH Sheet Resistivity (Ω/sq. P P P P P P&B P&B P&B Ni Sinter Temp (◦ C) 400-700 290 375 400 400 400 250 Photolithography and RIE Mechanically scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Laser scribed Ni Sinter Time (min) N/A 15 10 N/A N/A 5 10 Source          Table 2.) Activation Cell Type Contact 1 Etched 2 SSBC 3 EWT 4 SSBC 5 SSBC 6 SSBC 7 DSBC 8 DSBC 9 IBBC Cell Ni Height No.4: Summary of processing parameters of various c-Si solar cells with buried.1 5 0. (μm) 1 5 2 1 3 N/A 4 0.Cell No. 20 < B < 70 P < 5. B < 10 Ni Sinter Ambient Forming Gas N2 N2 N2 N2 N2 N2 Other Metal Thin AED Cu Electrolytic Ag AED Ni + Cu AED Ni (0. 25 .1 6 N/A 7 N/A 8 N/A 9 N/A † The unreacted Ni was removed after sintering. B < 10 P < 5. Dopant As 14 Heavy Heavy Heavy <5 P < 5. electrolessly plated contacts.
to reduce shading losses. Inhomogeneous Ni layers and blistering were found to be a problem during plating. however screen printed contacts made a better rear surface reﬂector . 7 and Cell No. 4. In plating Cell No. a silicide does not need to be formed in order to make . A Ni annealing temperature of 400◦ C was employed for Cell No.4. The electrolytic Cu bath composition of Cell No. 6. Sintering the AEDs of Ni at too low a temperature also caused adhesion problems while sintering at too high a temperature or in oxygen was found to cause Ni spiking. In EWT cells the emitter contact busbar is on the rear side and is connected to the front grid through via holes. This demonstrates that for a laser scribed. 4 and Cell No. 5 was varied to achieve bottom up ﬁlling of the grooves with no overplating and the cell IV characteristics were compared to the electrolessly plated Cell No. the IV characteristics of Cell No. however.6% have been achieved with this sintering temperature . This is the only application of this technique applied to solar cells that could be found in the literature. The DSBC Cell No. 8. Cell No. large area busbars (many scribes etched together) and laser drilled holes .1. As was the case with the furnace sintered cells in Section 2. The Ni annealing temperature for Cell No. The contact resistance and ﬁll factor were both slightly improved by switching to ﬁlled grooves . 3 did not ﬁt the 2-diode model which may also be due to the relatively high Ni sintering temperature of 400◦ C. EWT cells with AEDed contacts were found to have lower series resistances than the same cells with screen printed contacts. buried contact. because the series resistance of these SSBC cells was reduced by annealing at higher temperatures . 5 were plated using the technique of removing the unreacted Ni after silicide formation. Cells No. IBBC cells with adhesive contacts and efﬁciencies of 19.26 opening. 3 is an example of a laser scribed buried contact with a different structure an emitter wrap through (EWT) cell. . 9 was reduced to 250◦ C to avoid shunting between the base contacts and the emitter . 3. Here Ni is electrolessly plated simultaneously to ﬁngers (single laser scribe). with efﬁciencies almost as high as that of the IBBC. have been achieved without sintering the Ni at all . heavily P diffused busbars than in the ﬁngers and via-holes. it was reported that it is much more difﬁcult to obtain adhesive AEDs on the large area.
Examination of reports on Pd immersion activation reveals that this increases the nucleation density of susequent Ni deposits on p-type Si and thereby improves adhesion of the Ni layer. The plating rate. a review of the literature pertaining to the electroless metallisation of Si solar cells has been presented. 2. adhesion and resistivity of AEDs of Ni is reported to be related to the plating bath pH and plating temperature while the silicidation and adhesion of these deposits is reported to be related to the dopant density and orientation of the substrate. Adhesion was only reported to be an issue for some planar contacts and large area buried contacts.5 Summary In this chapter. . with both planar and buried contacts have been reported to have been successfully metallized by various electroless plating sequences.27 ohmic contact to heavily diffused Si or for the contacts to be adhesive. Many different solar cell structures. The most commonly reported problem with electrolessly plated cells was increased recombination or shunting due Ni sintering temperatures that were too high. The dopant density in an electrolessly plated. NiP alloy was reported to affect the phase of the silicide formed and Pd activation of the substrate was reported to inhibit the formation of Ni silicide.
3 and Section 3. Modiﬁcations to the SSBC that have the potential to signiﬁcantly improve cell efﬁciency have been worked on extensively at the University of NSW.4 demonstrate how a sulfuric peroxide mixture (SPM) is used in this thesis.3. is presented.3.2 3.1 Introduction In this chapter.1. Section 3. Section 3. A schematic of the SSBC is shown in Figure 3.2 discusses how Ni plated samples were sintered in this work. Constituents of the plating solutions are given in Section 3. Contact to the base is achieved through an Al alloyed region over the whole of the rear surface. It consists of a selective phosphorus emitter with laser scribed buried contacts on a p-type base. Section 3. The double sided buried contact (DSBC) solar cell . . 3.1 Background Information Buried Contact Solar Cell Structures The single sided buried contact (SSBC) solar cell was invented by Wenham and Green in 1985 . and has been in commercial production ever since.1. the method used to carry out the experiments of Chapter 4.2. Section 3. . and IBBC solar cell  utilise P and .3. .Chapter 3 Research Methodology 3.2 provides some information about the types of contacts found in buried contact solar cells and their usual metallization sequences.3.3 starts by discussing the test structures used in this thesis.
diffused to 100 Ω/sq. Figure 3. phosphorus emitter and passivated with SiO2 . 4) Ni and Cu plating in the front surface grid and 5) Ni and Cu plated over the entire rear surface. with phosphorus and passivated with SiO2 .1: Schematic of a SSBC solar cell showing 1) random pyramid textured. diffused with 100 Ω/sq. 4) laser scribed grooves. 2) laser scribed grooves. diffused to < 5 Ω/sq with phosphorus. rear surface. diffused with 100 Ω/sq. with boron and 5) Pd. front surface. diffused to < 5 Ω/sq with phosphorus.2: Schematic of a IBBC solar cell showing 1) random pyramid textured. 3) laser scribed grooves.29 Figure 3. diffused to < 10 Ω/sq. front surface. 3) random pyramid textured rear surface with an aluminium back surface ﬁeld. boron emitter and passivated with SiO2 . Ni and Cu plating in both rear grids. 2) saw damage etched. .
Both the DSBC and IBBC structures introduce heavily diffused boron grooves into the processing sequence in place of Al alloyed contact of the SSBC.1.1: IBBC solar cells processing sequence prior to metallization. The Al alloying step also serves as the PGD drive in and in the laboratory is performed for 15 hours (overnight) at temperatures of around 1000◦ C. This results in a sheet resistivity of less than 3 Ω/sq. The DSBC has a different structure to the IBBC but the contacts are virtually identical. The IBBC solar cell processing sequence is shown in Table 3. As previously shown . P2 O5 glass is deposited in the grooves at 940◦ C for 45 . B diffused surfaces with thermal SiO2 coatings to reduce the high rear surface recombination velocity associated with the Al BSF in the SSBC structure. there are several key differences between the SSBC and the IBBC structures. the requirements for deglazing the grooves on an IBBC cell are remarkably different from those on an SSBC . As can be seen from this and Figures 3. The base contact is formed by alloying an Al layer to the rear surface. It also leaves a phosphorus silicate glass (PSG) on the surfaces of the grooves which can be removed in about one minute in a NH4 F:HF (15:1) solution.1 and 3.2. A schematic of the IBBC is shown in Figure 3.2. The substrate of the standard SSBC is p-type and hence the selective emitter contact is achieved with a heavy phosphorus groove diffusion (PGD).60 minutes by solid source diffusion.30 Process Name Saw Damage Etch Texturing Front Surface Field Oxidation Rear Surface Prep Boron Emitter Oxidation Base Contact Scribing Base Contact Diffusion Base Contact Drive-In Base Contact Masking Emitter Contact Scribing Emitter Contact Diffusion Emitter Contact Drive-In Process Description 25% NaOH Solution 2% KOH/10% IPA Solution 100 Ω/sq P diffusion TCA dry oxide growth HF then 12% NaOH Solution 100 Ω/sq B diffusion Dry/wet/dry oxide growth Base contact glass deposition Diffuse P to 3 Ω/sq Dry oxide growth Emitter contact glass deposition Diffuse B to 10 Ω/sq Time 20 mins 20 mins 10 mins 60 mins 10 mins 20 mins 150 mins 60 mins 180 mins 60 mins 60 mins 180 mins Temperature 85◦ C 90◦ C 850◦ C 1030◦ C 55◦ C 900◦ C 980◦ C-1030◦ C 940◦ C 1050◦ C 1000◦ C 940◦ C 1050◦ C Table 3. that greatly effect the plating sequence.
This method proved inferior to electroless copper plating because it was difﬁcult to get the paste into the grooves and it left a residue on the surface which was particularly problematic in the case of textured wafers. Paste was deposited in the grooves but wiped off the ﬁeld oxide with the squeegee. proprietary. The metallization sequence for the original SSBC solar cell is reported as follows : 1. Residual PSG. that the deglazing solution for the IBBC needs to be signiﬁcantly different to that used for SSBCs due to the different etch rates of the various glasses involved . The Ni layer is sintered in a resistively heated.2 Plating Buried Contact Solar Cells Electroless metallization of SSBCs was initially employed because SSBCs made with screen printed pastes were unable to produce efﬁciencies as high as those with Cu contacts . The screen printed cells were fabricated by using a squeegee but no screen . 2. 3. in order to diffuse boron into the emitter contact. improve adhesion and act as a diffusion barrier to the subsequent Cu layer. Shrinkage and high bulk resistivity of the printed pastes also proved detrimental for the SSBC design and electroless plating was found by licensees of the technology to be so much more economical than screen printing that it offset the cost of the extra furnace diffusion associated with the selective emitter .2. which is present in the front contacts after phosphorus groove diffusion. is removed with a 15:1 buffered HF solution. electroless plating bath (from chemical supplier Transene ). It has been shown . . This is because.31 cell. A layer of Ni is plated conformally in the phosphorus diffused. The two groove diffusions result in the presence of a thick layer of boro-phospho-silicate glass (BPSG) in the phosphorus grooves and a boro-silicate glass (BSG) in the boron grooves. 3. quartz tube furnace at around 400◦ C to form a Ni silicide layer. a masking oxide must be grown over the phosphorus diffusion in the base contact. front contact grooves from an acid based. Ni also plates to the Si rich regions of the Al/Si alloyed rear surface. The silicide layer is made to reduce contact resistance.
2. DSBC and IBBCs have substantially different contacts. Ni is plated from an alkali based proprietary electroless plating bath (from chemical supplier Transene ) at 90-95◦ C. The metallization sequence for these cells. which was developed at UNSW. 1% NH4 F solution. Another Ni layer is then electrolessly deposited from the same Ni bath to ensure that the subsequent Cu layer will initiate. The thick layers of BPSG from the phosphorus grooves and BSG from the boron grooves is simultaneously removed with a 1% HF. from a proprietary electroless Cu solution (from Enthone ). 6. A layer of Ni is plated conformally in the phosphorus and boron grooves. Pd immersion solution. the plating sequence for the SSBC could not be used on the DSBC and IBBC solar cells. The PGD sequence for IBBC solar cells consists of the same P2 O5 glass deposition with a shorter drive-in time at a higher temperature. The sheet resistivity of this diffusion . There is also a masking oxide step and a B2 O3 deposition half way through the drive-in process. 5. The silicide layer is made to reduce contact resistance. is reported as follows : 1. 5. improve adhesion and act as a diffusion barrier to the subsequent Cu layer. The Ni layer is sintered in a resistively heated. A layer of Cu is electrolessly deposited in the phosphorus and boron grooves from a proprietary electroless Cu solution (from Enthone ). quartz tube furnace at around 250◦ C to form a Ni silicide layer. 3.32 4. The IBBC plating sequence is complicated by the requirement to plate Ni to both polarities of Si. Another Ni layer is then electrolessly deposited. Because the SSBC. A layer of Cu is electrolessly deposited in the phosphorus grooves and over the rear surface. to ensure that Cu will plate to the sintered Ni layer which may have become deactivated during the sintering process. Both groove types are activated with an NH4 OH-based. 4.
Several authors report. This activates the solution such that plating is much more likely to initiate on other. The entire rear surface of the SSBCs is covered in an Al/Si alloy.3 of this thesis. The two types of PGD are. is much smaller than on an SSBC cell and hence the metal plate does not always initiate. which has been observed previously  and which is conﬁrmed in Section 4. that over-plating of the ﬁeld dielectric became problematic when using Pd immersion activation . . dummy wafers) into the bath as well . The switch to an alkali-based electroless Ni bath was made during the development of the DSBC because it was thought to initiate better on the heavily boron-diffused grooves . a phenomenon also observed in this work (see Section 4. The total area to be plated on an IBBC cell. Pd activation was incorporated into the IBBC plating sequence to further improve the Ni plate in the boron grooves . smaller areas on the cell. however. such as the front surface grooves. . This resulted in a signiﬁcant improvement in the series resistance of IBBC cells activated with Pd but also an signiﬁcant drop in the shunt resistance. It was hypothesised that the reason for this was improved nucleation of Ni on the heavily diffused boron surfaces. The cells plated with Pd were ∼ 3% more efﬁcient (in absolute terms) than ones plated without Pd activation. In an IBBC cell the phosphorus grooves are used as the base contact and hence there is also no p-n junction present between the PGD and the base. particularly the Cu plating. . This is generally mitigated by adding something that is known to plate (eg: strips of Al. Another difference between the two structures that affects. however. usually thought to be similar enough to be plated in the same way.3). however.33 sequence is generally lower than that of the SSBC sequence and it is likely that the surface concentration is also different (although it is unclear whether it is higher or lower). This does not result in shading issues in back contact cells but it is a potential cause of shunting and is best avoided if possible. is the total surface area to be plated. on which plates both Ni and Cu.
2.34 3. Simpler test structures. This correlation could be tested by plating pit contact IBBC solar cells using the plating sequence developed in this thesis.2: Silicidation test structure types. Baker ) prior to electroless plating. the SSBC groove structure was included to enable sheet resistivity measurements of metal layers on a phosphorus diffused surface.3 and Section 4.2. along with their usual plating sequences. 15 hour drive-in 60 min P deposition. (100) p.cm. Alkali-based electroless Ni NH4 OH-based Pd Immersion. T.4 and Section 4. 5 hour drive-in Interface Plating Alkali-based electroless Ni NH4 OH-based Pd Immersion. This means that the silicide formation observed on these test structures is not necessarily the same as the silicide formation occurring on buried contacts scribed through the surface of a (100) wafers.and n. All planar test structures were deglazed until hydrophobic in a proprietary solution of 7:1 buffered HF (from chemical supplier J.3. Although this work focuses on plating IBBC cells. are outlined in Table 3.2. Alkali-based electroless Ni Table 3. which represent the three different groove types employed in buried contact cells. Cell Type SSBC IBBC IBBC Substrate p-type n-type n-type Groove Diffusion 60 min P deposition. a strong correlation between the observations of metal plating and sintering on the pit contacts in Section 4. Sheet resistivity measurements were carried out using a standard. .3 and the test structures in Section 4. There is. consisting of 1 Ω. Although the diffusion proﬁles on the test structures has been kept as close as possible to those found in buried contact cells. equispaced four point probe station.1. the orientation of the plated surface is different.3 Experimental Method All IBBC solar cells processed for this thesis were fabricated according to the sequence outlined in Table 3. 8 hour drive-in 20 min B deposition.type wafers with various diffusions types over the entire surface were also fabricated for this work. this affects the silicide growth rate from pure Ni deposits and possibly the phase transformations from AEDs of Ni.5. however. As discussed in Section 2. These structures.
99% 30-35% 30-60% 0-0.H2 O (NH4 )2 HC6 H5 O7 NH4 NH4 OH (EDTA) H2 O Amount 1 . The electroless Pd immersion solution employed on all structures is the NaOH-based bath (bath F) reported by Karmalkar et al.3. by volume. Constituents of the bath are detailed in Table 3. .35 3.10% < 1% Balance Table 3. proprietary electroless Ni plating solution from Transene . Plating was carried out at 80◦ C ± 2◦ C or 93◦ C ± 2◦ C.4: Bath constituents of a proprietary electroless Cu plating solution from Enthone .3: Bath constituents of an ammonia-based.10% 5 .01% Table 3. Ingredient Nickel Chloride Hexahydrate Sodium Hypophosphite Ammonium Citrate Ammonium Chloride Ammonium Hydroxide Ethylene Diammine Tetracetate Distilled Water Chemical Name NiCl2 . All were Ni plated in 300 mL of solution which was stirred using a teﬂon coated magnetic stirring rod and a stirring hot plate.6H2 O NaH2 PO2 . which consists of mostly deionised water with 1% HF and 1% NH4 F. Autocatalyitic electroless NiP deposits were plated from the alkaline based proprietary electroless Ni solution from Transene .10% 5 .1 Electroless Plating The deglazing solution used on all IBBC cells in this work is identical to the one reported in . .3. Ingredient Chemical Name Amount Enthone Cu704 A Copper(II) Sulfate CuSO4 Formaldehyde H2 CO Tetrakis-(hydroxypropyl) ethylenediamine (Quadrol) Enthone Cu704 B Tetrakis-(hydroxypropyl) ethylenediamine (Quadrol) Enthone Cu704 M Sodium Hydroxide Potassium Cyanide NaOH KCN 10-20% 10-20% 0-9.5% 1 .5% 5 .
the wafers are pulled into the mouth of the elephant and cooled on the furnace side of the N2 inlet to the elephant for around 3 minutes. Constituents of this bath are detailed in Table 3. where applied. Activation wafers were 4 cm x 4 cm and were roughened prior to plating such that both sides plated Cu over the entire surface. so that it saw a temperature of about 200◦ C. The other end is ﬂanged such that it ﬁts over the mouth of the furnace and there is a N2 inlet on the top. so that the wafers can be pulled passed the N2 inlet without breaking. It consists of a section of quartz furnace tube that is closed at one end except for a small hole to ﬁt a push rod through. quartz tube furnace ﬁtted with a quartz load lock known as an elephant. and was then unloaded into air. Sample (a) has been Ni plated but not sintered at all. was deposited from a proprietary solution Cu704 from Enthone .36 Autocatalytic electroless Cu. An elephant is used during furnace sintering of Ni plated layers because Ni oxidises readily in air at temperatures above about 200◦ C. 2% Cu704M and 86% deionised water. The N2 ﬂow to the elephant is then turned down momentarily. Sample (b) was loaded into the furnace without the elephant. One activation wafer was added to the Cu plating bath along with the samples in each plating run. resistively heated. 6% Cu704B. The N2 ﬂow is then turned up high and the elephant disconnected from the furnace. Figure 3.2 Ni Sintering All Ni sintering in this work was carried out in a 4”. The wafers are allowed to cool back to room temperature in the elephant for a further 5-10 minutes. After sintering.3.3. All Cu plating was carried out out at 46◦ C in a 300 mL bath made up of 6% Cu704A. Wafers are then pushed into the centre-zone of the furnace where they are sintered in a high N2 ﬂow rate with the elephant still attached to the mouth of the furnace. During this time N2 is kept ﬂowing through the inlet on the elephant to keep it as free of O2 as possible. It looks fairly similar to .4.4 shows how oxygen entering a furnace during sintering can be detrimental to the plated layer. to ensure that they cool to below 150◦ C whilst still in N2 ambient. Wafers are loaded into a parallel-loading quartz boat and pulled into the elephant. 3. by volume. The elephant is ﬂushed with N2 before attaching the elephant to the mouth of the furnace. A schematic of an elephant is shown in Figure 3.
Sample (d) was sintered in the same way as sample (c) except the furnace N2 ﬂow was greatly reduced. A parallel boat was used so that the wafers in a single experiment all see the same temperature gradient and the boat was positioned such that the wafers sat at a distance 80 and 85 cm into the furnace. Sample (c) was sintered in the same way as sample (b) except that it saw a temperature of about 400◦ C. The thermocouple used to measure the temperature proﬁle was only just long enough to just reach the ﬂat zone with the elephant connected. Temperature/position proﬁles for some of the sintering temperatures used in this work are shown in Figure 3. Prior to commencing this work. The Ni has gone an even darker gold colour and blue streaks have started to appear. Samples sintered at 500◦ C. the furnace used for Ni silicidation was temperature proﬁled with the elephant connected (the proﬁle was found to to be considerably different with and without the elephant attached for the same furnace settings). . with an elephant connected to the mouth of the furnace but the elephant N2 left off during unloading. have been observed to turn bright blue and sintering electroless plated Ni in a belt furnace (air ambient) at 400◦ C will result in a deep purple Ni coating.37 Figure 3. It is important that this does not happen during experiments as the effects of oxidation during silicide formation has not been studied. The temperatures quoted in this work are those shown on this graph and hence the actual temperature encountered by the samples is likely to be 10-20 ◦C higher than stated.3: Schemaitic of an elephant. The Ni has turned a dark gold colour.5. sample (a) but slightly yellowed.
The samples have been Ni plated and (a) no sintered. Figure 3. (b) sintered at 200◦ C without the use of an elephant.4: The effects of O2 on electroless plated Ni when heated. (d) sintered at 400◦ C without the use of an elephant and with the furnace N2 turned down.38 a) b) c) d) Figure 3.5: Temperature proﬁle of furnace used for Ni silicide formation . (c) sintered at 400◦ C without the use of an elephant.
HF is also effective at etching Ni oxides. Vacuum depositions of Ni are sintered by RTP at low temperatures to form thin layers of Ni2 Si. to remove copper oxide from electroless deposits prior to contact resistance measurements. HNO3 :HCl:H2 O (1:5:10) and HCl:H2 O2 :H2 O (1:1:60) solutions . The reaction between H2 O2 and H2 SO4 is exothermic. A proprietary. This solution can also be utilised as a selective etch at room temperature .3 Ni Cleaning Selective etching of unreacted metal from silicide contacts is commonly used in the IC industry where a two stage sintering process is employed to avoid shallow junction shunting . was also reported . . It has been clearly shown that unreacted Ni is etched away and the silicide is left behind after etching in a H2 SO4 :H2 O2 (4:1) solution at 60◦ C for 10 minutes . In this study. especially between different layers of metals. HNO3 was used as the etchant. an SPM cleaning solution is used to remove the unreacted Ni from sintered. The solution is 1:1 (v/v) H2 SO4 (98% ) and H2 O2 (30%). The wafers are immersed as soon as the solution is mixed and stirred for one minute. Cleaning the surfaces of plated metals is standard practice in the electroplating industry. H2 SO4 -based cleaning agent.3.39 3. before overﬂow rinsing. but is problematic for use on semiconductor devices as it will also etch SiO2 . One of these is acid immersion etching in either 500 mL/L of 37% HCl or 150 mL/L of H2 SO4 to remove any Ni oxide that might have formed on the surface . Good etching selectivity between Ni and Ni silicide has been achieved in H2 SO4 :H2 O2 :H2 O (4:1:60). Selective etching is also useful when studying the sheet resistance of the underlying silicide phase. Ni plated samples. . to promote adhesion. In this case. The unreacted Ni is then removed and a second RTP is performed to convert the Ni2 Si phase to the low resistivity NiSi phase. This gives a H2 SO4 :H2 O:H2 O2 ratio of approximately 4:2:1. and the solution heats itself to more than 100◦ C. The technique of selectively removing the unreacted Ni from the silicide contact in solar cells has also been reported . The American Standard for Testing and Materials (ASTM) for electroplating Ni to electroless Ni seed layers recommends various cleaning techniques.
The roughened swirls on section (b) are assumed to be areas where silicide formed but was then removed in the RCA2 etch.4 Pd Cleaning The Pd activation technique employed by Karmalkar et. Section (b) is grey with swirls of roughened areas whereas section (c) is covered with smooth grey and bronze swirls. Section a) shows the Ni plate intact. The grey areas are assumed to be the original surface of the wafer where silicide formation failed and the unreacted Ni was removed. Section (a) shows the Ni layer after sintering. in that the Pd is sintered at 200◦ C for an hour and a black residue is removed by swabbing the surface with a cotton bud soaked in isopropyl alcohol (IPA).6: Three sections of a boron diffused sample that has been Ni plated.6 shows a Si wafer that has been boron diffused to 100 Ω/sq and then Pd activated for 5 minutes. Figure 3. This selective SPM is utilised in the remainder of the experiments presented in this chapter. A Si wafer with a light boron diffusion (100 Ω/sq) was cleaned in the 4:2:1 SPM dis- . The sample was then split into three sections.3. section (b) shows the sintered Ni after RCA2 cleaning and section (c) shows the sintered Ni after SPM cleaning.40 a) b) c) Figure 3. Obviously this cleaning technique is not at all applicable to grooves or pits on solar cells. 3. Ni plated at 80◦ C for 4 minutes and sintered at 350◦ C for 10 minutes.  differs signiﬁcantly from that used by Guo in the IBBC plating sequence . al. These bronze sections can not be removed by repeating the SPM process and are assumed to be Ni silicide. b) shows the Ni plate removed with RCA2 and c) shows the Ni plate removed with SPM. so another cleaning technique was sought. to examine the silicide formation on planar test structures.
7 (b).3 discussed . as shown in the right half of Figure 3.4 Summary This chapter presented a review of the contact structures on buried contact solar cells and gave details the experimental methods used in the current work. A brown coating appeared on the wafer surface. Section 3. Section 3. The left side of b) has been swabbed with a cotton bud soaked in IPA and the right side has been SPM cleaned and then swabbed with a cotton bud soaked in IPA. cussed in Section 3.7 (a). Both halves of the wafer were then swabbed with a cotton bud soaked in IPA. There was no visible reaction at the wafer surface. 3. The same sample was HF dipped. as shown in Figure 3.7 (b).41 a) b) Figure 3. This indicates that the two processes (IPA swabbing and SPM cleaning) produce a similar result so the SPM Pd cleaning process was trialled in some of the experiments in Chapter 4.3. The wafer was split in half and one half was cleaned in the SPM. DSBCs and IBBCs and showed why Pd is necessary in IBBCs even though it can result in some overplating of the ﬁeld oxide. No black residue was able to be removed from the half of the wafer that was Pd activated and then SPM cleaned and yet the brown coating is still visible on the wafer surface. Bubbles evolved vigorously from the wafer surface. A black residue was removed from the Pd plated sample as shown in the left side of Figure 3.3.2 discussed the differences between contacts on SSBCs. rinsed and Pd activated for 5 minutes.7: A boron diffused wafer a) after Pd activation and b) the same wafer after cleaning.
Section 3.42 the use of samples in this thesis.3.3.1 gave details of the plating solutions used and outlined how the plating processes were controlled.3. Section 3.2 discusses process control for Ni sintering in a quartz furnace. Section 3.3 demonstrates how Ni silicide was observed on test structures and Section 3.3. .4 demonstrates how SPM cleaning of Pd activated samples has the same effect as swabbing the samples with IPA.
5.2.3. This is then conﬁrmed experimentally in Section 4. Adhesion problems encountered when pit contact IBBC cells are metallized using the standard plating sequence is discussed in Section 4. In Section 4. presented in Section 4.2. The ﬁnal experiment.4 phosphorus and boron diffused test structures are used to determine the effect of three different surface treatments .2. and Pd activation with SPM cleaning .on Ni silicide formation. demonstrates that the improved silicidation technique also improves the adhesion of thick. The results of a series of experiments that examine the effect of Pd activation and Ni plating parameters on silicide formation for the case of heavily phosphorus and boron diffused Si is then presented.1 demonstrates how the volume of heavily diffused Si in a buried contact solar cell is reduced by changing the laser scribing code from grooves to pits.3 examines the morphology of electrolessly plated Ni layers and the contact interface on a pit contact IBBC cell with and without Pd activation.no activation.2. with and without sintering. Pd activation.1 Introduction This chapter presents and discusses the experimental results of this thesis. The effect of Pd sintering and Ni plating bath temperature on silicide formation are also investigated in this section.Chapter 4 Experimental Results and Discussion 4. Section 4. electroless Cu layers on planar test structures. Section 4. An improved Ni silicidation technique is developed from these experiments. .
in all of the UNSW buried contact solar cell structures. or pits. 4. The geometry of the grooves does not allow them to be ﬁlled by the electroless plating sequence. thereby reducing the total number of recombination sites without increasing the barrier height between the metal and the semiconductor. the holes join together to form a trench. When the laser damage is etched away. the Cu ﬁngers are generally plated to a width of about 50 μm across the wafer surface. One way to achieve this in the buried contact structure is to reduce the strength of the groove diffusions. Nd:YAG laser in external mode causes the laser pulse to be triggered based on the position of the stage. using a 12% NaOH solution. To achieve a large enough volume of Cu in the grooves.1. Running a Q-switched. is formed by scribing a line of overlapping holes through the ﬁeld oxide on the wafer surface with a laser. If the laser . a solar cell grid pattern can be formed in a similar manner to a standard buried contact grid pattern except that instead of the ﬁngers consisting of trenches they will consist of a line of small holes. This allows for precise control over the spacing between laser ablated holes on the wafer surface. so as not to incur signiﬁcant series resistance losses. which may lead to resistance limited enhanced recombination . This is a thinner ﬁnger width than most screen printing processes achieve  but does not fully utilise the buried nature of the contact.2 Preliminary Experiments The main contribution to Jo in crystalline silicon solar cells with good post-processing bulk lifetimes is recombination in the heavily doped regions under the metal contacts. It has been shown that replacing large areas of heavy diffusion with locally diffused ones has a signiﬁcant impact on solar cell performance . The spacing between pits is controlled by the laser software.44 4. In order to reduce this contribution to the recombination current there needs to be fewer dopants in the diffused contact regions. Another way is to reduce the total area of the contacts. as shown in Figure 4. with a regular spacing.2. By utilising this feature of the laser. which is only 25 μm wide and extends 50 μm into the substrate. .1 Pits and Grooves: a Structural Comparison The trench-like structure of the grid ﬁngers.
2. The total area contribution for a standard tench-shaped ﬁnger can be approximated by the depth of the groove multiplied by the length of the trench multiplied by two (ie: two sides of the trench). ﬂoat ˚ zoned. Hence. A batch of n-type. buried contact device. Two interdigitated grids were then scribed on all wafers except one control wafer which had no grid pattern scribed on it. Hence the volume of metal carrying the current will be the same as in the standard grid structure but the total area of heavy diffusion within the cell will be signiﬁcantly reduced. over the oxide and join together in the middle. When cells with pit contacts are plated with the standard buried contact electroless metallization scheme. 75 μm and 100 μm and two were scribed with .2 Pits and Grooves: a Photoconductance Comparison An experiment was conducted to investigate the effect of reducing the volume of the total heavily-diffused Si in a well passivated.2 (the pyramids are inverted so the base is on the surface of the wafer). square-based pyramids with a 20 × 20 μm2 base as shown in Figure 4. This will be the total surface area of heavy diffusion per pit spacing. 1 Ωcm wafers were lightly diffused with phosphorus (to 100 Ω/sq) and a thick (3500A) thermal oxide was grown to passivate the surfaces. If the laser is operated at 532 nm. grow out of the pits. For pits with 10 μm square bases the total surface area is a quarter of this. the pits formed (after the usual NaOH groove etch) are inverted. plating will nucleate in the pits. Two samples were each scribed with pit spacings of 50 μm. The apex angle (the angle between the normal to the base through the apex and the facet) of a square based pyramid is 35. If the pits are spaced 50 μm apart and plated until they join together then the ﬁnger width will be 50μm.45 is operated with wavelength of 1064 nm. 4. a grid made up of square-based pyramids with a base length of 20 μm and a spacing of 50 μm will have 7 times less surface area within the substrate than the same shaped grid made up of 50 μm deep grooves.26◦ . Therefore. Hence the height of each facet of a pyramid with base length 20 μm is around 17 μm and the total surface area of a pit of this size is around 700 μm2 . the pits formed will have a similar shape but will be 10 × 10 μm2 on the base. a 50 μm long section of a 50 μm deep trench will have a total surface area of 5000 μm2 .
The pits are spaced 50 μm apart and hence the adjacent pits are out of the frame of this image.1: Ni and Cu plated 50 μm deep groove on an IBBC solar cell showing the void at the centre of the trench and 50 μm of overplating. . Note the oxide overhang in the plane view and the Si overhang in the cross section. The pits were scribed with a laser wavelength of 1064 nm and hence end up being 20 μm across. a) b) Figure 4.46 Figure 4.2: SEM micrograph of (a) the plane view and b) the cross section of etched pits. The border with rounded corners in the plane view corresponds to the Si overhang and there is no oxide overhang in the cross section because the oxide was thinner to begin with and hence got etched back to the edges.
In order to measure the effect of this. The I-Voc of each sample. It is not unreasonable to think that the main cause of increased series resistance in a pit-contact IBBC cell would be due to the same current being conducted into the contacts through a smaller area. Several attempts at this were made before it became clear that the main cause of series resistance in pit contact IBBCs is a lack of redundancy. This corresponds to an increase in I-Voc of approximately 10 mV.100 μm apart. a split batch of the two types of cells would have to be manufactured. These shows that a 25-35% reduction in Jo can be gained by replacing grooves with pits spaced 50 . at a carrier density corresponding to one-sun illumination and the Jo value of each sample. After diffusion of the scribed samples. can be converted into an implied open circuit voltage (I-Voc ). the transient and quasi-steady-state photoconductance decay (PCD) methods  were used to measure the injection-level dependent. Jo . It was envisaged that this 10 mV gain could be incorporated in to the IBBC structure by simply rewriting the laser code (ie: for no additional cost). The contact surfaces were then passivated with an oxide grown for 60 minutes at 1000◦ C.4. by the method outlined in . The P2 O5 deposition time was 60 minutes at 940◦ C and the drive in time was 3 hours at 1050◦ C in N2 ambient.2. obtained by curve ﬁtting. are plotted in Figures 4. A laser wavelength of 1064 nm was used for all samples. including the plating. at any carrier density. every pit must plate and join to the adjacent pits.) was then performed. To achieve high efﬁciencies with cells of this design. can be extracted. if the pits are spaced 50 μm apart. Laser damage was removed with a weak NaOH etch and a heavy phosphorus groove diffusion (∼ 5 Ω/sq. If just one pit fails. By ﬁtting the lifetime curves at the high injection end. effective minority carrier lifetime curves. All other processing would be identical to the standard IBBC. 4. respectively. The lifetime of the sample. the saturation current contribution of the diffused regions.3 Metal Adhesion Problems of Pit Contacts The main problem that could potentially arise from replacing groove contacts with pit contacts is series resistance.3 and 4. however.47 trench contacts. part or all of a ﬁnger will become disconnected .
4: Saturation current contribution from the diffused regions as a function of contact type. Figure 4. .3: Injection-level dependence lifetime curves of the various contact types.48 Figure 4.
The cells with groove contacts were plated until the ﬁnger width was 50 μm and cell efﬁciencies greater than 19% were measured. Several split batches of IBBC cells.7 shows one of the ﬁngers on another Cu plated cell. were fabricated (see Table 3. Arrow 4 points to three pieces of Cu with rounded tops and pyramid-shaped bottoms.2.2).49 Figure 4. The second and fourth ﬁngers have a heavy boron diffusion in the pits.5: SEM micrograph of poorly adhesive electroless Ni and Cu plated on the pits of several ﬁngers of an IBBC cell. as shown in Figure 4. however. Their shape indicates that they were plated in three adjacent pits and then came detached from the cell at some stage during the plating process. from the contact grid. which negates the potential beneﬁt of having the pits in the ﬁrst place.6 a) is an SEI of a busbar and part of a ﬁnger on a pit IBBC cell. There are at least ﬁve pits on each boron diffused ﬁnger that have no metal in them. Some of the pits in this image are over ﬁlled with Cu (arrow 1). some are half ﬁlled (arrow 2) and others appear to be empty (arrow 3). because the plating was unreliable. Only one in ﬁve pits on each phosphorus diffused ﬁnger is copper plated. . Figure 4. Figure 4. half with pit contacts and half with groove contacts. Efﬁciencies of the pit contact cells were unable to be measured.1 for processing details) and plated using the standard IBBC metallization sequence (see Section 3.5. at the point of adhesion failure. The ﬁrst and third ﬁngers (from left to right) have a heavy phosphorus diffusion in the pits. The ﬁrst and third ﬁngers are phosphorus diffused and the second and fourth ﬁngers are boron diffused.
Figure 4.6: a) A busbar on a pit IBBC cell showing how the Cu plating has fallen out of the pits and b) a close-up of the top left hand corner of the same busbar. The numbers refer to the pit to the right of the number.
Figure 4.6 b) is a close-up of the top left corner of the image shown in Figure 4.6 a). There are, in fact, three different types of pits on this sample (labeled 1, 2 and 3 in the image): Pit 1. pits with no metal in them, Pit 2. pits with Cu in them and Pit 3. pits with Ni in them. To ascertain that this is actually the case, an EDS map was made of the each of these pits (see appendix A for a discussion of SEM and EDS). An SEI of the mapped area and EDS maps of the Si, Cu and Ni signals for each pit are shown in Figure 4.8. It is clear from these images that Pit 1 has no Ni plated in it and only a small amount of Cu plated around the top corners. Pit 2 has a layer of Cu plated in it which is so thick that the electron beam can’t penetrate to the substrate (ie: there is no Si signal in the pit). This is also the case for Pit 3 except this time the Si signal is blocked by a layer of Ni. There are many points in the plating sequence that could be the source of metallization failure. The following discussion refers to the labeled arrows and pits in Figure 4.6. Arrows 1 and 2 point out that pits with Cu in them do not all have the same amount of Cu. There could be two reasons for this; 1) Cu initiates in the pits at different times during the plating sequence and 2) the Cu plated in some pits falls out at some stage during the plating process and then reinitiates. Arrow 4 points to evidence of this as does Figure 4.7. Arrow 3 and Pit 1 demonstrate that some pits have no metal plated in them. There could be several reasons for this; 1) neither the Ni nor the Cu plated in the ﬁrst place, 2) the Ni plated
Figure 4.7: A ﬁnger on a pit IBBC cell showing the Cu plate detaching from the Ni plate in the pit.
Pit 1. No Plating
Pit 2. Cu Plated
Pit 3. Ni Plated
Figure 4.8: SEIs and EDS maps of the pits labeled Pit 1, Pit 2 and Pit 3 in Figure 4.6 b).
52 and then fell out of the pit or 3) the Ni and the Cu plated and then both fell out together. The ﬁrst is unlikely as the Ni deposit on this sample was observed with an optical microscope before proceeding to the next step in the process. Not all the pits were examined but, of a random sample of pits across the wafer (including both contact pads), all were found to have Ni plated to them. It will be shown in Section 4.4.4 that the Ni sintering process can cause the unreacted Ni to peel away from the substrate. Therefore the second reason can not be discounted as the failure point. It will be shown in Section 4.5 that when Cu is plated to an unsintered layer of Ni, both layers of metal peel away from the substrate. Therefore the third reason can also not be discounted. Pit 2 shows that there are some pits that have Ni plated in them but not Cu. This could be because: 1) the Cu failed to initiate or 2) the Cu plated to the Ni and then adhesion failed at the Cu/Ni interface. Cu could fail to initiate on the Ni in a given pit if the surface of the Ni has become oxidised. This could happen after the ﬁrst layer of Ni is sintered, thereby causing the second not to plate. It could also happen after the second layer of Ni is plated but before the Cu initiates. In Figure 4.7 the Cu that has come away from the substrate is still attached to the Cu in the adjacent pit. It appears that there is a layer of Ni left behind in the pit it has fallen out of, however, the geometry of the sample does not allow for this to be conﬁrmed by EDS analysis. It is unlikely that the adhesion failed at the Ni/Cu interface, however, because, as will be shown in Section 4.5, the bond between Ni and Cu is quite strong. What is quite clear from this, is that the Cu is plating to many of the pits for a considerable length of time and then falling out. This is also quite surprising, given that the deposit from the same plating sequence applied to the standard groove contacts is always adherent, regardless of whether the Ni is sintered or not. This is most likely due to the way only a thin layer of metal plates on the walls of the grooves before the top is closed off, thereby physically holding the metal in place (see Figure 4.1). The geometry of the pits, on the other hand, allows the metal to fall out if the adhesion at any of the interfaces is poor. Determining which interfaces are poorly
Pit contact IBBC cells were fabricated and metallized in the manner outlined in Section 3. Various parameters in the metallization sequence were varied and a Cambridge 360 scanning electron microscope (SEM) was used to make secondary electron images (SEI) of the topography of the Ni plate.1 Ni Plated Pits Ni silicide formation has been shown to be inhibited by the presence of thin oxides at the Ni/Si interface . 4. A discussion of SEM and EDS can be found in Appendix A. if the phosphorus diffused pits are properly deglazed. The results of this investigation show that Ni has a low nucleation density on heavily boron diffused pits. phosphorus and boron groove diffusion test structures .53 adhesive is the subject of the rest of this thesis. This causes extreme roughening of the contact interface after sintering which has the potential to cause shunting problems in ﬁnished devices. The phosphorus test structure took twice as long to go hydrophobic as the boron test structure.3. The aim of the investigation was to determine whether or not the standard IBBC electroless Ni metallization and sintering sequence resulted in the formation of a silicide at the contact interface of pit contact IBBC cells. Hence.3. the ﬁrst step in a metallization scheme that employs silicide contacts. the boron diffused pits must be also. This means that. 4. Section 4.3 Metallization of Pit Contacts This section shows the results of an investigation of electroless Ni plating of pit contacts IBBC solar cells.3 shows that this problem can be mitigated by Pd activation. To determine roughly how long cell contacts should be deglazed for.9 shows Ni plated to a boron and a phosphorus diffused pit on a pit contact IBBC . is proper deglazing of the contact surfaces.that had been subjected to the same groove diffusion sequence as the cells .3. Energy dispersive spectroscopy (EDS) on the same microscope was used to conﬁrm the presence or absence of Ni in the pits.were deglazed in the cell deglazing solution. Figure 4.
54 solar cell. This cell was Ni plated at 90-95◦ C for 10 minutes after being deglazed for 9 minutes (with agitation). The Ni plate is not conformal on either pit type and much of the Si in the pits is still exposed. Another cell was deglazed for 12 minutes (with agitation) and subjected to the same Ni plating process. The Ni layer was totally conformal on the phosphorus contacts on this cell. A typical example is shown in Figure 4.10 a). The AED on the boron diffused pits, however, still suffers from low nucleation density of the Ni plate. A typical example of this is shown in Figure 4.10 b). It is clear that the phosphorus diffused pit has been adequately deglazed which means the boron diffused pit must be also. Therefore, the low Ni nucleation density seen here must be a feature of the heavily boron diffused Si. a) b)
Figure 4.9: An example of badly deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni.
Figure 4.10: An example of well deglazed a) phosphorus and b) a boron diffused pits, plated with electroless Ni.
Ni Sintered Pits
To examine the interaction of Ni and Si at the contact interface after silicidation, a pit
contact IBBC solar cell was split into three sections and two of the sections were plated with Ni at 90-95◦ C. One of the plated sections was sintered at 350◦ C for 10 minutes, to form a Ni silicide on the walls of the pits. The third section was not plated at all. The two plated samples appeared identical to the pits shown in Figure 4.10. Ni plating on the phosphorus diffused pits was conformal but on the boron diffused pits it was lumpy. Sintering did not change the appearance of the Ni plate; the sintered and the unsintered sample were practically identical. The plated samples were then etched in a standard RCA2 metal etch to remove the unreacted Ni. Figure 4.11 a) shows a pit on the sample that was not plated and Figure 4.11 b) shows a pit on the sample that was plated but not sintered. The Ni plate has all been removed in by the RCA2 process and the two pits appear almost identical. This indicates that there is not much interaction between the plated metal and the Si substrate, either during plating or removal of the metal in RCA2. This result was the same on both phosphorus and boron diffused pits. Figure 4.12 a) shows one of the phosphorus diffused pits on the sintered sample after removal of the Ni with RCA2. The Ni is now absent from this pit also and there has been some roughening of the pit walls in comparison to Figure 4.11 b). A Ni signal was not detected by EDS on any of the phosphorus pits. A boron diffused pit on the same sample is shown in Figure 4.12 b). A signiﬁcant Ni signal was unable to be detected by EDS in any of the boron pits either. As discussed Appendix A, this could mean there is no Ni present or that the amount of Ni present is too small to be detected by the microscope. It was shown in Section 3.3.3 however, that the etching selectivity of this process is low, which has most likely resulted in all the Ni being removed from the pits. Hence, Figure 4.12 shows that sintering the conformal Ni plated to phosphorus diffused pits - Figure 4.10 - causes minimal changes to the Ni/Si interface but sintering the uneven plating on boron diffused pits - Figure 4.10 b) - causes extreme migration of the Ni/Si interface. The mechanism behind this is not known and an investigation into it’s
56 causes has not been attempted here. It is likely to cause shunting, however and should be avoided. The next section shows how this effect can be avoided by increasing the nucleation density of the Ni plate on heavily boron diffused pits. This is achieved by Pd activation. a) b)
Figure 4.11: Pit contacts that have a) had no plating at all and b) been Ni plated at 90-95◦ C and the Ni removed in a standard RCA2 etch (no sintering).
Figure 4.12: An a) phosphorus diffused and b) a boron diffused pit that has been Ni plated at 90-95◦ C after sintering at 350◦ C and removal of the excess Ni in RCA2 solution.
Pd Activated Pits
It is hypothesised here, that rough plating in boron pits is a result of low nucleation
density of Ni on heavily diffused, p-type surfaces. To determine whether this is the case, another pit contact IBBC cell was properly deglazed and activated with Pd for 2 minutes (with agitation), rinsed with DI-water and then immediately plated with electroless Ni. The Ni plating used here was reduced to 80◦ C to avoid spurious overplating of the ﬁeld oxide, an example of which is shown in Figure 4.13. It was found previously, that overplating of the ﬁeld oxide was able to be
3. Ni plated sample was split in half and one half was sintered at 350◦ C for 10 minutes. The Ni plate in the boron diffused pits is much more conformal than when no Pd was used. IBBCs with grooves .1 shows a summary of these results.15 shows two of the pits on the sintered sample after the Ni has been removed in RCA2. Migration of the Ni/Si interface is now much more moderate. It should be noted that Pd activated. indicating that the nucleation density has increased signiﬁcantly. The interaction between the Ni and the phosphorus diffused surface. however. Table 4. that may lead to junction shunting.1 and 4. This causes extreme migration of the Ni/Si interface upon sintering. Figure 4.3.57 eliminated by reducing the Ni plating temperature from 95◦ C to 90◦ C for Pd activated.3 is that the nucleation density of AEDs of Ni.3 onto heavily boron diffused Si.2 because heavily boron diffused pits are unable to be plated in the Transene Ni solution at 80◦ C without Pd activation.3. is quite low. pit contact IBBC cells plated with Ni at 93◦ C suffered the same adhesion problems as those plated at 80◦ C. that poor silicide . pit con- tact IBBCs becomes more moderate with Pd activation. A higher Ni plating temperature was employed in Sections 4. It was found in this work. The Pd activated. Pd activation promotes a more conformal AED of Ni and moderates the interface migration.4 Ni Silicidation Section 4.4 Conclusions The main conclusion of the experiments presented in Section 4. however. The nucleation density on heavily boron diffused contact regions can be increased by Pd activation. is also a lot more moderate than on the unactivated samples. from the alkaline based bath outlined in Section 3. It is possible then. 4. 4.3 showed that the interaction of Ni and Si at the interface of sintered. that spurious overplating was an issue for pit contact IBBCs for Ni bath temperatures above 83◦ C.14 shows Ni plating on two of the pits on the unsintered sample and Figure 4.
a) b) Figure 4. a) b) Figure 4.14: A well deglazed.58 Figure 4.13: Ni plated onto the ﬁeld oxide.15: The Pd activated a) phosphorus and b) boron diffused pits after sintering and RCA2 to remove the unreacted Ni. Pd activated a) phosphorus and b) boron diffused pit. with Pd activation and electroless Ni plating at 80◦ C. The bottom left pit is plated with Cu but all other pits and the areas between them were determined to be Ni by EDS mapping. .
Deglazing followed by NH4 OH-based Pd activation followed by SPM cleaning. As discussed in Section 2.3 formation may be one of the causes of low adhesion on pit contact IBBC solar cells. employed in the standard IBBC and/or the Pd activation may be inhibiting the silicide formation and contributing to adhesion failure on the pit contact IBBC cells.  (as discussed in Section 3.3 to remove any unreacted Ni. 2.3) were varied prior to electroless Ni plating.3.3. Deglazing followed by NH4 OH-based Pd activation (as found on IBBC grooves). different phases of Ni silicide form at different temperatures above about 200◦ C and each phase has a different resistivity. Deglazing only (as found on SSBC grooves). so that the Ni silicide formation could be observed. Surface preparation Number 3 was introduced to mimic the process reported by Karmalkar et al. 3. 4. .4). Silicidation was carried out by furnace sintering as described in Section 3.3.59 Pit Type Phosphorus Phosphorus Phosphorus Boron Boron Boron Pd × × × × Ni Smooth Smooth Smooth Lumpy Lumpy Smooth Sinter × × Interface Smooth Uniform roughening Less roughening Smooth Extreme roughening Uniform roughening Table 4. It is hypothesised here that the low sintering temperature of 250◦ C. In order to study silicide formation.2.4.1 Effect of Surface Activation This section describes an experiment designed to test the effect of sintering temperature and surface preparation on silicide formation. the interface conditions of the three planar test structure types (outlined in Section 3.3. The wafers were then SPM cleaned using the method discussed in Section 3. Three different surface preparations were tried: 1.1: Summary of results from Section 4.
The SPM-cleaned sample became partially hydrophobic. The sample without Pd became totally hydrophobic and the Pd-activated sample remained hydrophilic. These images show that the SPM-cleaned samples are all mostly bronze in colour but the samples with and without Pd appear the same colour as they did before the Ni processing.2. Four sets of three samples were prepared in this way and the sintering temperature varied from 250◦ C to 450◦ C in 50◦ C intervals. All SPM-cleaned samples and samples without Pd plated uniformly bronze and all Pd-activated samples plated cloudy (grey). Before is therefore the sheet resistivity of the heavy phosphorus diffusion and After . The samples with Pd have some small bronze areas but the samples without Pd exhibit virtually no bronzed areas at all. The average sheet resistivity across each sample is shown in Table 4. After Ni sintering. The sheet resistivity of the SPM-cleaned samples was measured before and after the whole plating/silicidation process.16. the samples were plated with Ni at 80◦ C for 4 minutes. One of these samples was SPM cleaned and then all three samples were HF dipped again. The surface of the wafers after the ﬁnal SPM clean (to remove the unreacted Ni) are shown in Figure 4. The Ni plated samples were then sintered for 12 minutes and the unreacted Ni removed by SPM cleaning. Without Pd HF dip Pd Activation SPM HF Dip Ni plating Sinter SPM × × With Pd With Pd and SPM × Table 4. After surface preparation.60 Three SSBC (phosphorus diffused) test structures were HF dipped until hydrophobic and two of them were then Pd activated for 2 minutes until hydrophilic. A summary of this procedure is shown in Table 4. The appearance of the Ni plate was quite repeatable for all four runs.2: Summary of the experiment. all samples were SPM cleaned to remove the unreacted Ni.16. The results are shown in Figure 4. water clung to the surface for a few seconds before dispersing to leave the wafer hydrophobic.3.
2 Ω/sq 2.3 Ω/sq 400◦ C 2. It is beyond the scope of this thesis to perform more precise qualitative analysis (Auger spectroscopy.2 Ω/sq 2.7 Ω/sq 300◦ C 3.16 it was concluded that a reasonable coverage of silicide can be obtained on phosphorus diffused surfaces at temperatures above 300◦ C. Boron diffused surfaces require Pd activation without SPM cleaning .indicate that these bronzed areas are Ni silicide. Both the Pd-cleaned sample and the sample without Pd failed to plate. The Pd activated sample plated well and a silicide formed over the entire surface. Silicide formation for these conditions was then investigated on boron diffused surfaces. None of the samples without Pd formed a silicide at all and silicide formation on samples that were Pd activated was minimal.5 Ω/sq Before After Table 4.3 Ω/sq 0. inability of the bronzed areas to be etched by SPM cleaning and a lowering of the sheet resistivity in the bronzed areas but not in the grey areas . for instance) of the surface.61 250◦ C 3. the sheet resistivity decreased. Three boron diffused test structures were prepared in the same manner as the SSBC samples. if the surface is Pd activated and SPM cleaned. is the sheet resistivity of the Ni silicide layer and the heavy phosphorus diffusion in series. Measurements were taken before the plating sequence (ie: this is the sheet resistivity of the phosphorus diffusion). a fairly uniform silicide formed over most of the surface and coverage exhibited a slight temperature dependence.3 Ω/sq 0. Based on Table 4. but three factors . and after the unreacted Ni had been removed (ie: this is the resistivity of the phosphorus diffusion and the Ni silicide in parallel). On all samples.bronzed areas on the wafer surface that are visible to the naked eye. patchy and independent of silicidation temperature.16 shows that in order to get reasonable silicide coverage with these plating and sintering conditions. however. the Si surface ﬁrst needs to be Pd activated and SPM cleaned.3: Sheet resistivity variation with Ni sintering temperature. On the samples that were Pd activated and SPM-cleaned. indicating that the surface has changed.6 Ω/sq 450◦ C 2. Figure 4. These results show that for these plating and sintering conditions it is not possible to form a silicide at the contact interface on both heavily phosphorus and boron diffused planar <100> surfaces at the same time.
across the whole surface. .16: P-type substrates with SSBC PGD of 3 Ω/sq. The samples had different Pd treatments prior to electroless Ni plating at 80◦ C for 4 minutes. The samples were sintered for 10 minutes at the temperatures indicated and the unreacted Ni removed in a 50% SPM.62 Without Pd With Pd With Pd and SPM 250◦ C 300◦ C 400◦ C 450◦ C Figure 4.
al. Based on Table 4. Table 4... Examples of uniform and non-uniform Ni silicide on Pd sintered samples are shown in Figure 4.4 a Pd sintering time and temperature of 20 minutes at 250◦ C was chosen to test both IBBC diffusion types.  . Six boron groove diffusion test structures were deglazed until hydrophobic and then Pd activated until hydrophilic (4 mins). because it resulted in the formation of a uniform .4. The unreacted Ni was again removed by SPM cleaning so that the silicide formation could be observed. It should be noted that boron test structures were not able to be plated at either Ni plating temperature without Pd activation. The samples were then SPM-cleaned and a vigorous reaction was observed on all samples.63 in order to plate and the phosphorus diffused pits require Pd activation and SPM cleaning for a silicide to form. suggesting that Pd was still present on the sample surface. 4. Karmalkar et.4. This section describes an experiment conducted to determine whether the formation of a Pd silicide prior to Ni silicidation. The samples were plated with Ni at 93◦ C for 4 minutes and sintered at 300◦ C for 10 minutes to form a Ni silicide.4 shows that Pd sintering enables subsequent Ni silicidation on boron diffused test structures even after SPM cleaning. All boron test structures prepared with sintered Pd were able to be plated.2 Effect of Pd Sintering In their studies. improves the formation of a Ni silicide on heavily phosphorus diffused samples.17. sintered their Pd seed layers prior to Ni deposition and then cleaned the remaining residue from the sample by swabbing. It would appear that Pd silicidation was successful at temperatures as low as 200◦ C and that a longer sintering time results in a more uniform Ni silicide at any temperature since the same swirly patterns that were visible in the Pd plate were also visible in the Ni silicide. Each sample was sintered with different time and temperature parameters. It also demonstrates the importance of a nitrogen ambient during sintering. as shown in Table 4. The higher plating temperature was used here because it was found that cells plated in this manner did not suffer from spurious overplating. however.
One test structure of each diffusion type was deglazed and activated with Pd for 3 minutes (until both samples became hydrophilic).17: Boron groove diffused samples that have been Pd activated and the Pd sintered for a) 10 minutes at 250◦ C and b) 40 minutes at 200◦ C. Ni silicidation again failed on the phosphorus diffused sample.4. It was found that if this cleaning step is included.1 showed that in order to form a silicide on heavily phosphorus diffused samples it was necessary to ﬁrst activate with Pd and then clean off the black residue with SPM. The samples were then HF dipped and plated with Ni at 93◦ C for 4 minutes and the Ni sintered at 300◦ C for 10 minutes. a Ni plating temperature of 90◦ C . as before.4: Pd sintering on boron diffused test structures. Ni silicide in a reasonable time. A uniform silicide formed across the surface of the boron diffused sample.3 Effect of Ni Plating Temperature Section 4. 4.64 Sample 1 2 3 4 5 6 Temperature 200◦ C 200◦ C 200◦ C 250◦ C 250◦ C 300◦ C Time 20 min 20 min 40 min 10 min 20 min 10 min Ambient AIR N2 N2 N2 N2 N2 Pd Silicide Swirly Swirly Swirly Swirly Swirly Swirly Ni Silicide None Swirly Uniform Swirly Uniform Swirly Table 4.95◦ C can . is in fact removing the Pd.18 shows images of the silicide formed by this process. The Pd was sintered at the chosen conditions and the two samples were SPM cleaned. Figure 4. Both samples then underwent SPM cleaning prior to Ni plating and at 300◦ C.4. a) b) Figure 4. The unreacted Ni was removed with SPM. the unreacted Ni was removed in SPM. This and the fact that the boron diffused samples do not plate without Pd and that a silicide does not form on the phosphorus diffused samples with Pd suggests that the black residue removed in the SPM cleaning process after Pd activation. Finally.
The resultant silicide is shown in Figure 4. boron samples. The coverage is more uniform for the longer sintering time. Silicide . Two major differences in silicide formation were observed on samples plated at 93◦ C compared to those plated at 80◦ C.2). The samples were sintered at 350◦ C for 5 minutes and the unreacted Ni removed with SPM. The experiment was repeated on IBBC phosphorus and boron diffused test structures but with a lower Ni sintering temperature of 300◦ C for a longer time (10 minutes).20.2. The ﬁrst is that a silicide now forms on the SSBC PGD sample without Pd activation and the second is that the Pd activated/SPM cleaned. The boron test structure with no Pd failed to plate but all other samples plated. IBBC BGD sample now plates and a good coverage of silicide is obtained. It is desirable to use a higher plating temperature if possible because the resistivity of the NiP alloy will be lower due to a lowering of the phosphorus content (see Section 2. Silicide formation on the phosphorus samples is shown in Figure 4. be used. Both Pd activated. An experiment was carried out to determine the effect of higher plating temperature on Ni silicidation on each of the three test structures. A silicide formed on both Pd activated. phosphorus diffused test structures still fail to form a silicide. Pd and SPM).18: Silicide formation on an a) IBBC phosphorus and b) boron test structure that was Pd activated and the Pd sintered at 250◦ C for 20 minutes. Pd. One sample of each test structure type was prepared with one of the three surface preparations (no Pd.65 a) b) Figure 4. with and with out SPM cleaning and on both the unactivated and SPM cleaned phosphorus sample but not on the phosphorus sample that was Pd activated. Pd activation was carried out for 3 minutes and Ni plating was done for 4 minutes at 93◦ C on all samples. The same result was observed on both sample types. without overplating the ﬁeld oxide (in a cell).19.
a previously unreported phenomenon was observed. Figure 4.4 Unreacted Ni During the course of these experiments on planar test structures. The picture has been taken at an angle and the semi-circular patterns are layers of Ni that are peeling away from the surface as the . The sample was then sintered at 300◦ C for 7 minutes. Pd activated.21 shows a wafer that was diffused to 100 Ω/sq with boron. The samples were sintered at 350◦ C for 5 minutes and the unreacted Ni removed in a SPM.4. 4. coverage on both the boron samples that plated was also uniform.20: IBBC phosphorus diffused test structures with three different surface treatments prior to electroless Ni plating at 90-92◦ C for 4 minutes.66 Without Pd With Pd With Pd and SPM Boron NO PLATE SSBC Phos IBBC Phos NOT TESTED Figure 4. SPM cleaned and plated with Ni at 90◦ C. The unreacted Ni spontaneously peeled away from the surface of the test structures upon removal from the elephant when cooled.19: The three different test structures with three different surface treatments prior to electroless Ni plating at 90-92◦ C for 4 minutes. The samples were sintered at 300◦ C for 5 minutes and the unreacted Ni removed in a SPM. Without Pd With Pd With Pd and SPM IBBC Phos Figure 4.
4 has examined the conditions required to form a Ni silicide on heavily phos- phorus and boron diffused. Once all the Ni has ﬂaked off.5. it has been observed during this work that one potential source of adhesion failure of electroless plated layers is Ni ﬂaking after sintering and that adhesion on pit contact IBBC cells might be improved by removal of the unreacted Ni after silicide formation.4. It is difﬁcult to observe Ni ﬂaking off 10 x 10 μm2 pits. a uniform coating of Ni silicide can be observed on all areas where ﬂaking occurred.2. This is the main ﬁnding of this thesis. The Ni was observed to curl up from the surface of the sample for at least ten minutes after being removed from the elephant after being cooled in the manner described in Section 3.4. <100> surfaces. 4. so chemically removing any unreacted Ni after sintering and prior to further metal deposition may need to be incorporated into the pit plating sequence. It is concluded that Pd activation in conjunction with SPM cleaning and high temperature Ni plating is the only surface preparation and plating sequence that will lead to Ni silicide formation on both heavily boron and phosphorus diffused surfaces simultaneously.67 Figure 4. This phenomenon typically happens on heavily phosphorus diffused samples and it only happens in areas where silicidation has been successful.3) are summarised in Table 4.5 Conclusions Section 4. Additionally. The plating and sintering results of this investigation (from Sections 4. . The cause of the ﬂaking Ni in not known but quite clearly such behaviour could lead to poor adhesion of subsequent plated metal layers. This was conﬁrmed by SPM cleaning and sheet resistance measurements.21: A photograph of Ni ﬂaking off a test structure after sintering at 300◦ C for 7 minutes.3. picture is being taken.4.1 and 4.
In the current work it was found that the adhesion of Cu layers plated to Ni layers on Si could be improved by Ni silicidation. If not it will come away on the tape. demonstrate the relative adhesion strengths between samples.5: Summary of results from Sections 4. The Cu plating method used is described in Section 3. It does.1. A piece of commercially available. which involves soldering a tab onto the contact and measuring the force required to pull it away from the cell.4. It was also found that the Cu/Ni bond is strong but that the stress within the .5 Cu Plated Layers Many of the Ni plated test structures that were made during this work were subsequently Cu plated. Previous studies  have shown that high stresses can be encountered within AEDs and that bath additives can reduce this stress (for the case of Ni pyrophosphate baths). however. If the metal/silicon interface is more adhesive than metal/tape interface the metal will remain on the wafer. The free end of the tape is then doubled back over the wafer and pulled off again parallel to the wafer surface.3 4. as will be shown in Section. so that the adhesion of the metal layers could be observed. Adhesion of plated layers was observed by conducting a tape test. This method of adhesion testing is not as rigorous as the industry standard pull test.68 Diffusion Plating Temp 80◦ C 90◦ C 80◦ C 90◦ C 80◦ C 90◦ C 80◦ C 90◦ C Without Pd With Pd Pd and SPM Appearance of the Ni Plate Phosphorus Phosphorus Boron Boron Bronze Bronze None None Cloudy Cloudy Cloudy Cloudy Bronze Bronze None Bronze Coverage of Ni Silicide Phosphorus Phosphorus Boron Boron 10% 80% N/A N/A 10% 10% 100% 100% 100% 100% N/A 100% Table 4.4.1 and 4.3. clear scotch tape is stuck to the plated surface and smoothed down to remove any air bubbles.
This was true of samples that were Ni plated with and without Pd activation and SPM cleaning steps. a) b) Figure 4. It was concluded from this that the Ni/Cu interface is more adhesive than the Ni/Si interface. SPM cleaned. HF dipped and plated with Ni . The tape tested layer was itself tape tested to see if the two layers of metal could be pulled apart. the internal stress is greater than the strength of the .69 Cu layer during deposition is so great that both the Cu and the Ni layer will spontaneously peel away from the substrate unless the Ni layer is anchored to it by the formation of a silicide at the interface. the as- plated (ie: not sintered) Ni layer was unable to be peeled away in a tape test. The samples were then Cu plated at 46◦ C for 1 hour. As the Cu layer becomes thicker. however. 4. both metal layers spontaneously peeled off the substrate surface (ie: came away from the surface and fell off without the use of any external force such as tape or drying in a stream of nitrogen).5.1 Without Ni Silicide When the test structures used in this work were plated with thin layers of Ni. When Cu was plated to the thin Ni layer. The Cu layer is not at all adherent to the sample surface regardless of the plating temperature of the initial Ni layer. When tape tested. the Cu layer came away from the sample easily.22: Cu plated layers on phosphorus diffused IBBC test structures that were ﬁrst plated with Ni at a) 80◦ C and b) 90◦ C. with the Ni layer clearly attached to the other side of it (the Cu and the Ni are different colours). Figure 4. which they could not.sample a) at 80◦ C for 4 minutes and sample b) at 90◦ C for 3 minutes.22 shows two IBBC PGD test structures that were Pd activated for 3 minutes.
SSBC PGD samples were plated as described in Table 4. With an activating dummy in the bath.2.5. The three. other . as shown in Figure 4. Instead of deglazing the entire surface. An interdigitated grid pattern was formed on one side of each wafer which had a line width of 400 μm with a 200 μm spacing between ﬁngers. A different pattern was formed on the other side of each wafer which consisted of 10 evenly spaced ﬁngers with a line width 120 μm and a spacing of 31 mm. however.2 With Ni Silicide To test the effect of Ni silicidation on the adhesion of subsequent AEDs of Ni and Cu. One wafer was diffused between each pair of solid sources so that the diffusion would be the same on both sides of the wafer.6. Figure 4.5.23. This was eventually achieved by adding NaOH and an activating dummy wafer to the Ni plating bath. the masking oxide was patterned photolithographically. three SSBC PGD test structures were made. patterned.70 Ni/Si bond and so the plated layer fails at the Ni/Si interface.23: Cross sectional schematic of the photolithographically deﬁned pattern used in Section 4. 4. Each line was 25 mm long. The two samples that were SPM cleaned after Pd activation had to be Ni plated three times before Ni initiated on the surface. It is believed that this was the result of a non-optimal boron diffusion. Photolithographically patterned IBBC BGD test structures were also made but these were not able to be Ni plated either with or without SPM cleaning after Pd activation.
The sheet resistivity of the Ni plated and sintered layer in series with the diffused layer was lower than Sample 1 2 3 Pd 3 mins 3 mins 3 mins SPM × HF Ni 4 mins 4 mins 4 mins Sinter Temp 300◦ C 300◦ C 400◦ C SPM + HF × Table 4. The results are shown in Table 4. a) b) c) Figure 4.6: Ni plating and sintering parameters for three SSBC PGD test structures with photolithographically deﬁned contacts. After the initial Ni deposition. .7.24: Plan view of two SSBC PGD test structures that were photolithographically patterned and metallized. Sheet resistance measurements were made on the grid pattern of Samples 2 and 3 at three stages during the metallization process: after oxide removal. both samples were sintered at 300◦ C for 10 minutes and the unreacted Ni was a) left on and b) removed in an SPM before further processing.71 samples from the same batch plated on the ﬁrst run. This illustrates the unreliable nature of electroless plating. The sheet resistivity of the diffused layer was the same on both samples. after Ni plating and after SPM cleaning of the sintered contact.
24 shows plan and tilted views of the resultant AEDs of Cu on a) Sample 1 and b) Sample 2. This conﬁrms that a silicide has been formed and that the SPM cleaning process has removed the unreacted Ni.13 1. adhesive layers of electroless Cu is problematic.45 0. Less metal was able to be removed in the tape tests on Sample 3 than on Sample 2. A difference in the resistivity of the silicide layer formed at each sintering temperature was not signiﬁcant in comparison to the total resistivity of the stack. The bottom left hand corner of the grid and all of the thinner gridlines on the other side of the sample came away in the tape test.3 Conclusions Plating thick.) Sample 2 Sample 3 2. Figure 4. The sheet resistivity is different to that of both the diffused layer and the Ni layer before the SPM cleaning process.5. Sample 1 was not dried with the nitrogen gun as the metal is obviously not adherent to the surface. It can be concluded from the experiments in Section 4. This is either due to a difference in the thickness of the silicide layers or difference in the phase of the silicide or both. Stress in the electroless Cu ﬁlm during plating causes adhesion failure at the Sheet Resistivity (Ω/sq. Sample 3 had the same appearance as Sample 2. all three samples were Ni plated at 93◦ C for 2 mins and Cu plated for 4 hours. Sample 2 was dried with a nitrogen gun and tape tested prior to imaging. A difference in the sheet resistivity was found however after removal of the unreacted Ni. This is probably due to stresses encountered within the plating layer.94 2.94 1.7: Sheet resistivity measurements of the various layers formed on photolithographically deﬁned contacts. . After SPM cleaning Samples 2 and 3. No tape test was needed for this sample because the entire grid came away during handling revealing that there was no silicide present on the wafer surface. 4.13 1.77 PGD Ni × × Silicide × Table 4.5 that the Cu/Ni bond is stronger than the Ni/Si bond (where the Si <100> and heavily doped). Sample 2 was sintered at 300◦ C and Sample 3 was sintered at 400◦ C. indicating that Ni was indeed present.72 that of the diffused layer.
For pit contact IBBCs it was found that this could be mitigated by lower the Ni plating temperature to less than 83◦ . This shows that a lack of silicide in the phosphorus contacts may be the cause of adhesion problems in pit contact IBBCs.2. however. On Pd activated samples.5. there is a potential for it to ﬂake . however. These Cu plating bath parameters are known to provide sufﬁcient Cu deposition for the pits on a pit contact IBBC solar cell.4 shows that when the unreacted Ni is left in the contact after silicidation.1.3 shows that Ni plated to heavily boron diffused pits without Pd can cause excessive Si migration during sintering. with a spacing of 50 μm. The cause of the adhesion problem is identiﬁed and a possible solution developed in Section 4. Section 4. Problems encountered during the electroless metallization of cells with the new grid design were presented in Section 4. If the samples are plated with Pd and then SPM cleaned prior to Ni plating.3. results in overplating of the ﬁeld oxide. both metal layers peel away from the substrate.5 shows that when Cu is plated to a Ni layer where a silicide has not been formed or silicidation has not been successful. It was shown that IBBC cells with a pit contact grid pattern should have a higher open circuit voltage than those with the standard grooves. causes Ni to fail to plate to BGD test structures and Ni silicide to fail to form on PGD test structures that are not Pd activated.3 to Section 4. however. both types of samples with plate and Ni silicide will form on both.2. explain the adhesion problems with the boron contacts. 4. to plate together to form a contact grid.4 shows that lowering the Ni plating temperature.2. Section 4.6 Summary Design of a new contact grid structure for IBBC solar cells was presented in Section 4. The use of Pd.2. Section 4. Section 4. The potential beneﬁts of this design were presented in Section 4. With the right processing parameters. silicidation of the Ni layer can improve the adhesion of the Cu layer to the point where it is still adherent after 4 hours of plating at 46◦ C. It does not however.4. Ni will plate to either type at low and high Ni plating temperatures and a silicide will form on BGD samples but not on PGD samples.73 Ni/Si interface.
should improve the adhesion of the electroless metal layers on pit contact IBBC solar cells.one after Pd plating and one after Ni sintering . which could be causing adhesion problems on both contacts. .74 off. Adding two SPM cleaning steps .
It is also shown in this work that it is difﬁcult to metallize pit contact IBBC solar cells with the standard IBBC electroless metallization scheme. experimentally. The purpose of the new design is to reduce the volume of heavily diffused material within the cell. . In order to form an electroless Ni silicide on the heavily boron and phosphorus diffused Si present in an IBBC device. A signiﬁcant reduction in the volume of heavily diffused material can be achieved by replacing the trench-shaped grooves of an IBBC solar cell with lines of inverted pyramids. Ni plating must ﬁrst be initiated on the diffused surfaces. to be: • The type of the dopant atoms at the substrate surface .Ni was found to have a lower nucleation density on boron diffused samples than on phosphorus diffused samples. otherwise known as pits. This aspect of the metallization scheme was not examined in this work. thereby reducing its contribution to Jo . a new contact design for IBBC solar cells is introduced and examined. This is because pit contacts suffer from initiation and adhesion problems that do not affect cells with laser scribed grooves. It is shown here that this modiﬁcation to the existing contact design could potentially lead to a 25-35% reduction in Jo and a 10 mV increase in open circuit voltage.Chapter 5 Conclusion and Future Work In this study. This thesis shows that poor silicidation is the main factor affecting adhesion. Initiation problems are probably due to the reduced area of the plating surface. The factors effecting Ni initiation were found.
regardless of the plating temperature.450o C the main factors effecting the silicide formation on p. It is possible that this potential adhesion problem only affects planar samples and does not occur on pit contacts but this would be difﬁcult to verify.a silicide was unable to be formed on unactivated n-type surfaces that were plated at 80o C even though Ni was deposited on the surface. several factors may still inﬂuence the silicide formation.76 This can lead to lumpy Ni deposits or no deposits at all. • Pd Cleaning . In the temperature range 250o C .inclusion of a SPM cleaning step after Pd activation resulted in silicide formation on both p.and n-type surfaces for a Ni plating temperature of 90o C. • The Ni Plating Bath Temperature . Once the surface is plated. • Pd Sintering . It was only observed to occur on areas where Ni silicidation had been successful however. It was also found that it is possible for the unreacted Ni to spontaneously ﬂake off planar samples after Ni silicidation. • Pd activation .if the Pd is sintered prior to this cleaning step.the nucleation density on p-type surfaces increases with activation leading to more uniform Ni deposits and deposits forming on p-type material at lower plating temperatures.deposits with a low nucleation density were found to change the morphology of the Ni/Si interface when sintered.diffused surfaces were found to be: • Morphology of the Ni Plate .this was found to inhibit silicidation on n-type surfaces but not on p-type surfaces. A silicide was found to form on unactivated n-type surfaces when the Ni plating bath temperature was increased to 90o C. • Pd Activation . This phenomenon was not observed on all samples and its cause is unknown. silicide coverage is greatly reduced on the n-type surfaces. depending on the plating temperature. so SPM cleaning prior to .and n.
however. The second clean follows Ni silicidation to remove any unreacted Ni that may be spontaneously peeling from the silicide surface. The next step of this investigation would be to implement the new metallization scheme on pit contact IBBC cells.type contacts. The ﬁrst clean follows Pd activation to allow the formation of Ni silicide on both p. If such cells can be fabricated by electroless plating. of the underlying silicide also affected the adhesion of the plated layers. Adhesion of the plated layers in this work was studied by electroless Cu plating. a study of Ni silicidation times and temperatures could be conducted to determine the minimum temperature required for adequate adhesion. Adequate adhesion of the second Ni plated layer. were able to be obtained for a Ni sintering time and temperature of 10 minutes and 350o C. Including such a step in the metallization sequence. The properties. It might be instructive to analyse the deposition from the Pd immersion solution on heavily diffused n-type and p-type Si. and hence of the Cu layer.and n. It was shown that the adhesion of the second Ni plated layer is signiﬁcantly improved by ﬁrst forming a silicide at the Ni/Si interface.77 the second Ni plate would negate its effect whilst still retaining the Ni silicide layer. respectively. Determining the composition at the surface . means that adhesion between the second Ni layer and the silicide needs to high. This thesis has shown that electroless metallization of pit contacts IBBCs is problematic. Hence. It is possible that the different surface dopant concentrations result in Pd layers with differing compositions. A comparison of the contact resistance of plated pit and groove type contacts would also make an interesting study. It was shown that a metallization scheme that might be able to successfully plate pit contact IBBC solar cells is the same as the standard scheme but it includes two SPM cleans. the most likely problem to arise is shunting of the base grooves to the emitter due to the increased silicidation temperature. not just the presence. Many issues pertaining to Ni silicide formation were identiﬁed and the rectiﬁcation of these issues was shown to improve adhesion of Ni and Cu plated layers on test structures. Contact resistance may also be an issue in pit contact cells due to the reduced contact area.
. It is clear from the literature that the formation of Ni silicide from AEDs of Ni has not been well studied. Such a study could also incorporate an investigation of the selectivity of various etchants on the phases of the silicides formed. heavily phosphorus diffused Si but is enhanced after Pd activation and SPM cleaning. There is much scope for XRD analysis and correlation of sheet and contact resistances of Ni silicides formed in this way.78 before and after the SPM clean (after the activation step) may provide insight into why Ni silicide does not form on Pd activated.
The black spectrum was measured at a lower magniﬁcation than the grey one. This shows that it is not easy to use EDS for quantitative measurements. It is possible. which yields a large Si signal and a small Ni and P signal. Ni and P maps are shown in Figures A. however. Maps of pits on the same sample are shown in Figure A.2 a). however.1 shows typical X-ray energy spectrums for a typical AED of Ni deposited from a Ni bath at 80o C.Appendix A SEM and EDS The pit contact solar cells plated in Section 4. Maps were made of Ni plated to pits on a pit contact IBBC cell. A larger signal can be generated from the smaller peaks by reducing the scanned area (increasing the magniﬁcation). The Si. . It is a useful qualitative technique. c) and d). It would appear from this measurement that all the Ni has been removed by the RCA2 solution. A secondary electron image (SEI) showing the topography of the mapped area is shown in Figure A.2 b).3 after sintering and RCA2 cleaning. for conﬁrming the presence or absence of different materials. Figure A. respectively. The SEM/EDS system can also be used to make qualitative X-ray energy maps.3 were imaged using a scanning electron microscope (SEM) and analysed by energy dispersive spectroscopy (EDS). that the Ni silicide layer makes up such a small proportion of the interaction volume of the beam in the sample that it can not be detected by this technique.
c) the Ni signal and d) the phosphorus signal. a) b) c) d) Figure A. b) the Si signal. c) the Ni signal and d) the phosphorus signal.2: X-ray maps of a Ni plated pit.1: X-ray spectrum generated on a Ni plated pit at low magniﬁcation (black spectrum) and at high magniﬁcation (grey spectrum). a) the SEI image of the mapped area.3: X-ray maps of a pit where the Ni has been sintered and the unreacted Ni removed with RCA2. . b) the Si signal. a) the SEI image of the mapped area. a) b) c) d) Figure A.80 Figure A.
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