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    cleaning technology of silicon wafers

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    6 views8 pages

    8309

    Uploaded by

    Pieter Robaeys
    cleaning technology of silicon wafers

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    NIPPON STEEL TECHNICAL REPORT No. 83 JANUARY 2001 Cleaning Technology of Silicon Wafers Abstract ich UEMURA Teun HAIBARA ‘eshiro MOR High quality wafers are in demand, as increasingly high integration of VLSIs became a commercial practice. This is especially true with highly clean wafers with little metallic impurities and particulate and organic matters on the surface. For producing the highly clean wafers, it is necessary to establish wafer surface clean- ing technologies through experimental and theoretical analysis of the behavior of the surface impurities. This paper explains adhesion mechanisms of metallic and particulate impurities to silicon wafer surfaces and proposes some cleaning meth- ods. 1. Introduction Increasing integration density of LSIs (large scale integration cir- cuits) call for higher quality silicon wafers. Higher quality wafers ‘mean the superior quality in crystal precision, shaping quality, and surface quality. Problems concerning chip size increase and manv- acturing cost increase must be considered. Practical application of '300-mm wafors has been discussed in recent years. Extremely high ‘surface cleanliness is required of the 300-mm wafers” (reer to Fig. 1), Specifications for organic impurities have begun tobe prescribed ‘as well as traditional impurities such as metals and particles. These ‘impurities are generated from wafer manufacturing equipment, chemicals, human bodies clean room materials, dust-free garments and reaction products, and are often deposited on the wafer surfaces ‘They cause interconnect failures and crystal defecs, then degrade Deine) Fig. 1 Relationship between device design rule and required wafer surface cleanness" “1” Testnieal Development Bureau “61 the device performance. For this reason, the surface cleanliness of silicon wafers is continuously improved. "To meet these requirements, itis important to theoretically ana- |yze the phenomena tha are taking place on the silicon wafer sur- face and to perform the process design on the basis of the results of the theoretical analyses. This report especially deals withthe adhe- sion mechanisms of metas and particles tothe wafer surface, and in- ‘woduces new cleaning methods besed on our theoretical examination, 2, Adsorption mechanism of Metals to Silicon Wa- fer Surface Since iron on silicon wafer surface causes crystal defects and degrades device performance, as much oft should be removed as is possible. Henley etal” indicated that an iron contamination level of 10" em” is required fora gate oxide thickness of 8 nm. Like iron, ‘other metals (€., nickel, chromium, copper, zine, and sodium) de- {grade the device performance (or change the transistor threshold Values, induce erystal defects to degrade the p-n junction leakage and pate oxide integrity, or accelerate oxidation). They must be re- ‘duced to meet shrinking device sizes. To remove these metals or to contol their adsorption in the cleaning Solution, it s necessary to understand their behavior in the cleaning solution. "Two major mechanisms are present for metal adsorption inthe leaning solution. One is chemical absorption, as is represented by the adsorption of metals to native oxide (SiO, in an alkaline solu- tion. The other is electrochemical adsorption to bare Si in an acidic solution, To understand these mechanisms, we conducted ionic equi- NIPPON STEEL TECHNICAL REPORT No. 83 JANUARY 2001 [ibrium analysis and electrochemical analysis, The results ofthese stugles are discussed below. 2.1 Tonic equilibrium analysis ‘An NH,OH+H,0,+H1,0 mixture (APM), also called “Standard Cleaning solation I (SC-I)" which i a representative alkaline clean- {ng solution, has such an extremely excellent particle removal capa- bility that itis widely vsed®. However, if metal ions exist inthe clean- {ng solution, they adsorb on the wafer surfae®. Especially, iron, when present even ina trace amount less than parts per billion (pp), de- ‘grades the electrical performance such as recombination lifetime, It poses a serious problem when itis caried over from the previous processor when low-purty chemicals are used. Metal adsorption in the SC-1 cleaning solution was traditionally ‘explained using metal oxide formation enthalpy or a complex ion ‘model, but was rarely discussed quantitatively. An analysis of the issue was tied according tothe chemicel equilirium theory”. Inthe SC-1 cleaning solution, formation of native oxide (Si0,) by hydrogen peroxide and etching of SiO, by alkalis proceed atthe same time, For this reason, the overall wafer thickness is slowly re- ‘duced, but a certain thickness of SiO, exists on the wafer surface, inrespective ofthe time. In this case ifthe etching ais slow enough 1nd the metal adsorption and desorption reactions are fast enough, & ‘certain metal ion adsorption equilibrium holds between SiO, and the solution. Actually, since te etching rate of SiO, by the $C-I clean {ng solution is afew mono-layers per minute” while the adsorbed amount of metals reaches @ constant value within one second after ‘wafer immersion, this equilibrium may be considered to hold. The relationship between the metal on concentration in the solution and the adsorbed amount ata given temperature is called “adsorption isotherm’. Fig. 2 shows adsorption isotherms fora 1:1:5 mixture of 29% ammonium hydroxide, 31% hydrogen peroxide, and de-ion- Jed water, andthe temperature of 80°C, Here, the ionic equilibrium in the solution is focused on. For 2 ‘metal jon denoted by Mf, the following chemical equilibrium holds inthe SC- cleaning solution: M+ OH'= M(H) M(OH)" + OH" = M(OH),"* M(OH), “+ OH= M(OH),"* ‘The existing proportion of metal hydroxide complexes denoted by .M! to M(OH),**is a function of pH and can be theoretically caleu- lated if each equilibrium constant is given", ‘The results of calculation for Fe in a concentration of 1x 10" ‘mol/l. (about 05 ppb) are shown in Fig. 3), Since the pH of the ‘SC-I cleaning solution is about pH 10.6 (for 1:1:5 proportion), the Fig. 2 Adsorption isotherms of Fe", NP, and Zn in SC-1 solution (138, 80°C) +62 nr \\ eseiotnoit ISN 25810 7eatt= ASA creme Fig. 3 pH dependence of Fe hydroxide complexes isting proportion of hydroxide complexes is Fe(OH), > Fe(OH), > Fe(OH), > Fe(OH? > Fe in decreasing order. From tis sul however, it eannot be eietyconluded ta he sored spies in the SC- leaning sluion s FOH), Ifthe reaction iin chemical equilicum, th adsorbed emount depends on the prac the con- entation and adsorption equbrium constant ofeach complex (if complex exists in a small amount bt ely large in equilibrium Constant, it can become a main adsorbed species). A further study was mad o identify the adsorbed species. Fe(OH), a hydroxide complex of Fe witoot charges can dis solve nan aqueous solution to eran concentration, but becomes sold and precipitates when texcedsthe erie eancentation d= termined by the solubility product. The dissolved species and solid species are denoted by FH), (aq) and Fe(OH), (5) respecively {oq ands sand fr aghoots and sol, respectively), The results of {hecaleltion including the formation af the sali species se shown inFigs. 306) and (c) When the Fe concentration reaches bout 5 10" mol, Fe(OH), 5) sas to form, When Fe is ded to higher concentration, the concentration ofthe other dissolved hydroxide complexes saturates in the pH range of 41011 "The caleslated concentration of Fe(OH) aq) a pH = 10.6, (ot responding tothe pH of te SC lenin ston, is shown in Fig 4), The measured adsorption isotherm of Fes shown in Fig (5) ‘The star of formation of Fe(OH) almost coincides with the start of saurstion ofthe adsorbed amount of Fe, This means that the Adsorbed species is one ofthe dissolved hydroxide species Fe(OH) aq) ater than the solid species Fe(OH), (). The finding thatthe sole species isnot he adsorbed species supported by the mmessoroment by tal-refiestion x-ray Muorescene spectroscopy COXRE. Tig § shows the TXRF angle-scan measurement results fora wafer produced inthe region where the sli species Fe(OH) x NIPPON STEEL TECHNICAL REPORT No. 83 JANUARY 2001 i a = ol i | t i i a Fe xem a) Fig. 4 Comparison of calculated values of FOF), (aq) concentration {@) and measured values of Fe adsorbed amount (b) tthe pH or 10s eye) ‘Gancae sete) Fig. 5 Comparison of TXRF angle-sean measurement results of wafers with Fe adsorption in Fe(OH), (5) formation region and non- Fe(OH), (6) formation reglon formed and for a wafer produced inthe region where the Fe(OH)(s) {snot formed, The verical axis indicates normalized maximum val- ves. The TXRF angle-scan profile depends on the depth distribution of analyte elements. The dissolved species and solid species are con- sidered to adsorb inthe bulk of SiO, in film form and on the surface (of SiO, in particle form, respectively. Ite slid species adsorbs, the angle-Scan profile should be diferent from that obtained wien the dissolved species adsorbs. In actual data (Fig. 5), both profiles al- ‘most agree with each other. This may be taken to mean thatthe solid species does not adsorb, ‘The above-mentioned experiments show thatthe adsorbed spe- cies is one ofthe dissolved hydroxides. When Fig. 3 is looked at here again, the pH dependence ofthe existing proportion ofthe hydrox- ide complexes varies with each other. Ifthe pH dependence ofthe adsorbed amount is measured and compared with te calculated val- tes, the adsorbed species can be identified. By adding tetramethy- lammonium hydroxide (N(CH,) OF, TMAH) tothe SC-1 cleaning solution, the pH was changed in the range of 10.5 ro 12, and the pH dependence of Fe adsorption was investigated. The results are shown in Fig. 6. ‘The slope inthis pH range was ~0.56 in linear approximation. ‘The slopes expected from the chemical equilibrium calculation are given for each dissolved species in Table 1. When x = 3, the caleu- lated value agreed best withthe measured valve. This means that the main adsorbed species isthe neutral hydroxide complex Fe(OH)(aq) dissolved inthe SC-I cleaning solution. The greatest likelihood of, neural hydroxide complexes o adsorb is supported by the theoret- -63- ot Fig. 6 pH dependence of adsorbed amount of Fe, Ni and Zn ‘Table 1 Comparison of pH dependence for adsorbed amount and for hydroxide complex concentration ‘eesured value | Caleoledvaloe wit expen MOA) 00) (Slope at pH= 1055-12) we! [x2 [xed | xe 036 | 338 | -238 | -138 | 038 | Oa si ost | 27g | 1.78 | -078 | 4022 | 1.22 zo 4013 | -268 | -1463 | -063 | +037 | +197 cal calculation proposed by RO. James etal. for metal adsorption. [Ni and Zn were also studied. These metal ions are known to react ‘with ammonia to form extremely stable ammine complexes. The ‘existing proportions of various complex species calculated by con- sidering the formation of the ammine complexes are shown in Figs. “Tand 8, From these diagrams, it can be seen that most of Ni and Zn exist as aramine complexes inthe SC-1 cleaning solution (pH = 106. ‘Table 2 shows the critical concentration, calculated from the solu- bility product of Ni(OH),(s) and Za(OHD,(s), at which these species ‘stato precipitate It is evident that the Ni and Zn contaminant con- centrations never reach the critical concentration forthe formation m Yes Fig. 7 pH dependence of Ni hydroxide and amine complex foncentrations oe cone ) Fig. 8 pH dependence of Zn hydroxide and ammine complex ‘concentrations NIPPON STEEL TECHNICAL REPORT No. 83 JANUARY 2001 ‘Table? Ammine and hydroxide complex concentrations in ammonia- ‘eal solution TS oe oi spina sgn by MOM.) 'EMINH(ag) | EM(OH G9) | EM(OH),) qootty | cmottey | emote NE | bao 710" =I za | bein sci <0! ofthe respective solid species in usual, This isthe eason why the _dsorpion isotherms of Ni and Zn do not level off Fe does in Fig. 2. ‘By measuring the pH dependence of the sorbed amount for Ni and Zn in the same manne as Fe, it maybe possible to identity the adsorbed species, The measured values are shown in Fg. 6, andthe calculated values are given together with those for Fe in Table 1. For [isthe calculated values agreed best wih the measured values when 1n=2. This suggests that the adsorbed species isthe neueal hydrox- {de complex Ni(OH), (aq) dissolved in the SC-1 cleaning slution as noted for Fe. Zn des not show any match between calculated and ‘measured values. This may be explained by formation ofthe poly- ‘clear complex Za,(OHD,” inhibitor effet of TMAH, or satura- tion ofthe adsorbed amount, buts identified yet. ‘According othe above results, itisblieved thatthe adsorbed species are not ammine complexes but hydroxide complexes also for Ni and Za, To substantiate ithe adsorption behavior of Nin a solution, which doesnot contain ammonia, was investigated The ‘I of the system was adjusted with potassium hydroxide (KOH) in place of ammonia, andthe pH dependence ofthe adsorbed amount ‘vas measured. The esl are also shown in Fig. 6. he adsorbed ‘mount was larger by mare than one order of magnitude than when ‘ammonia was contained. This i probably because a large amount of hydroxide complex, which is considered to he the adsorption spe- cles, was formed. Te adsorbed amount, however, ineeass only by ‘one or to orders of magnitude (egans si to nine orders of magai- tude expected from Fig. 7) and exhibits no pH dependence. This may be because the adsorption sits are ssturated From the above discussion, it was found thatthe adsorbed spe- cies in SC-1 solution i neutral hydroxide complex dissolved inthe solution. This finding canbe puto use in developing methods for reévcing meal adsorption inthe SC- cleaning soltion. For example, lowering the pH to reduce the existing proporion of Fe(OH, (ag) may prevent the Fe adsorption. Or adding a chelating agent that forms a stable complex with Fe(OFD, (aq canals be effective. 2.2 Metal adhesion mechanism in acd solution Acid cleaning solutions ae excellent in meu removal charac- terse, but the adesion of Cu and Au is considered problematic in solutions, such asa Slaton of ited hydrofluoric acid". These adhesion behavior ae explained by using the ionization tendency. Given the conduction type, resistivity and anion effect, however, it is ficul to explain them simply by the ionization bebavioe alone ‘To suppor this thinking, th adhesion behavior of metals in acidic solutions by electrochemical technique was analyzed’ The results ar introduced here. Firs, the relationship between the pH of the solution and the metal adhesion amount is described. In this ease, the recombination lifetime was examined by the b-PCD method to

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