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THE ROLE OF LOW-ENERGY ION/SURFACE INTERACTIONS DURING CRYSTAL GROWTH FROM THE VAPOR PHASE
J.E. GREENE. A. ROCKETf. AND J.-E. SUNDGREN
Materials Science Department. the Coordinated Science Laboratory. and the Materials Research Laboratory University of Illinois. Urbana. Illinois. 61801
Low-energy (often < 100 eV) ion bombardment during thin film deposition is commonly used in such diverse application areas as microelectronics. optical coatings. magnetic recording layers. and hard wear resistant coatings to modify the microstructure and microchemistry of films deposited by a variety of techniques (e.g. sputtering. primary ion deposition. plasma-assisted CVD. and accelerated-beam MBE). Ion irradiation has been shown to affect every phase of deposition including nucleation and growth kinetics. crystal structure and phase stability. the average grain size and degree of preferred orientation of polycrystalline films. the epitaxial temperature of single-crystal films. defect concentrations. elemental incorporation probabilities. surface segregation. and. hence. film properties. As discussed in this brief review. a detailed understanding of many of these processes is beginning to emerge. Effects such as trapping. preferential sputtering. enhanced diffusion. and collisional mixing have been used to interpret and. in some cases. model experimental results. Nevertheless. there are still large gaps in our knowledge of the role of ion bombardment on fundamental processes such as nucleation kinetics.
The requirements of increasingly sophisticated thin-film device and processing technologies have resulted in a continuing drive to obtain better control over the microchemistry and microstructure of as-deposited layers and to devise lower-temperature growth techniques. Unfortunately. these objectives are often mutually exclusive. Nevertheless. a general strategy has emerged involving the evolution of growth techniques away from near-equilibrium deposition toward kinetically-limited processes. With good experimental design and an understanding of the rate-controlling steps and reaction paths. the crystal grower can manipulate the growth kinetics to tailor the resulting film properties. (Clear evidence that this is possible is provided by recent results demonstrating the growth of new single-crystal thermodynamically metastable semiconductor alloys such as (GaAs)O_x/Ge,)x and (GaSb\_x(Ge2)x which exhibit non-linear optical properties [1.2].) General approaches which have been explored include the use of lowenergy ion bombardment of the film and photo-stimulated gas-phase and surface reactions during deposition. The first approach is discussed in this article while photo-stimulated reactions are reviewed in reference 3.
Low-energy (often < 100 eV) particle bombardment during vapor-phase deposition has been shown to play an important and sometimes dominant role in controlling film growth kinetics and physical properties. Ion-irradiation-induced effects have been observed in films deposited by glow discharge and ion beam sputtering. primary ion deposition (PID). plasma-assisted chemical vapor deposition (PA-CVD). and molecular beam epitaxy (MBE) using accelerated dopants. Applications include: film densification and enhanced oxidation resistance in optical films. minimization or elimination of columnar microstructure in metallization layers used in electronic devices. altering the state of stress. average grain size. and preferred orientation. increasing film/substrate adhesion. enhancing conformal coverage. controlling the magnetic anisotropy in recording layers. "lowtemperature" epitaxy. stimulating surface chemical reactions during deposition (and etching). tailoring film composition. the growth of metastable phases. and increasing dopant incorporation probabilities while decreasing segregation-induced broadening of dopant profiles in MBE grown Si and III-V semiconductors.
The effects of ion bombardment during film deposition. while often beneficial. are complex and pervasive. A desirable result is often achieved at the expense of introducing several other effects (some of which may be deleterious in a given application). Nevertheless. a detailed understanding of many ion-bombardment-stimulated processes is beginning to emerge and effects such as trapping. preferential sputtering. enhanced diffusion. and collisional mixing can be used to interpret and. in some cases. model experimental results. However. as discussed below. there are still large gaps in our knowledge of the role of ion bombardment on fundamental processes such as nucleation kinetics.
MaL ge s Soc. Symp_ proc. Vol. 74. 19B7 Materials Research socretv
II. NUCLEATION AND THE EARLY STAGES OF FILM GROWTH
There have been many reports in the literature over the last 10 to 15 years. summarized in recent review articles [4.51. on nucleation studies involving low-energy ion irradiation during deposition. The experiments have been carried out by a variety of means including: evaporation in which a portion of the evaporant stream is ionized and accelerated to the substrate using an external electric field (e.g. ion plating. in which most of the ions are due to the support gas. or PID from solid-source ion guns). evaporation in the presence of a separate ion source which provides the accelerated particle bombardment. and sputter deposition or PA-CVDwith the application of a substrate bias. Depending upon the deposition technique. there are. in addition to ions which are purposely accelerated to the substrate. other energetic particles such as secondary electrons. ions reflected (generally as neutrals) from a sputtering target. photons. and sputtered species incident at the substrate and growing film. (While the average ejection energy of sputtered particles under typical deposition conditions is - 5-15 eV. there is a high energy tail in the sputtered atom velocity distribution extending well above this range .) To complicate matters further. much of the early work in this field has been carried out in low to medium vacuum conditions and the experiments were often not well controlled.
At least part of the effect of ion irradiation during nucleation and growth experiments performed in medium vacuum is due to "sputter cleaning" of the substrate." (Donahue and Rief  have argued. for example. that this effect played a major role in allowing the growth of epitaxial Si at temperatures as low as 650 ·C by PA-CVD from SiH.). However. depending upon the film/substrate combination. the energy Et and flux J1 of incident particles. and the growth temperature T,. additional consequences of ion bombardment may be important. Examples include the production of defects in the substrate surface which can act as preferred adsorption sites." trapping or implanting of incident species in the near-surface region. recoil collisions resulting in the trapping of adsorbed species into higher hinding energy sites. the dissociation of small clusters during the early stages of growth. enhanced adatom diffusion. and local electric field effects due to charging.
The number density of active ion-irradiation-induced preferential nucleation sites will be determined. irrespective of the formation mechanism. by the difference between the production rate. which is a function of Et.J,. and the ion/substrate species. and the loss rate due to annealing (which increases with increasing T,) during deposition. Krikorian and Sneed  have shown. for example. that ion irradiation can be used to either increase or decrease the nucleation rate dnidt of Ge depending upon the choice of T, and the substrate material.
One of the first studies of the role of incident energetic species during three-dimensional (3-0) nucleation was carried out by Chapman and Campbell  who used high energy (40-50 keY) Ar and Xe ion beam sputtering to deposit Au onto NaCl(100) at T, between 30 and 310 ·C. They reported an increase in the maximum number density nmax of Au islands and an enhancement in the degree of (100) preferred orientation compared with results for thermal evaporation. Lane and Anderson [10.11] also reported increases in nmax for Au sputtered using a 2 keY Ar ion gun on cleaved NaCI at T. - 130-325 ·C. The latter authors fitted their results using classical nucleation theory with additional terms to account for the production of preferred adsorption sites with an increased binding energy. They assumed that these more strongly bound sites were due to defects produced in the NaCI substrate surface by bombardment with fast sputtered atoms. Harsdorlf and Jark [12J have used an analogous argument to explain increased dn/dt and nm .. values obtained for rf sputtered Au vs evaporated Au films on cleaved NaCI substrates maintained at 270-360 ·C. Sputtering was carried out in He at 30 mTorr and the authors used magnetic fields to suppress electron and ion irradiation of the substrate. However. as in the previous experiments. this still did not eliminate bombardment by energetic particles reflected from the target.
* Note that ion irradiation can also lead to Increased substrate contamination due to dissociative chemisorption. particularly in the presence of high background pressures of hydrocarbons.
*" Alteration of nucleation kinetics through the production of preferred adsorption sites was originally proposed to explain increases in nucleation rates. enhanced preferred orientation. and decreased epitaxial temperatures observed for metal films deposited on ionic substrates which were either previously or Simultaneously irradiated with energetic electrons or photons. The preferential adsorption sites were shown to be charged surface vacancies. (See discussion in references 4 and 5). Similar effects are expected for covalently bonded substrates.
Hassan et a1. (13) have recently begun to investigate primary ion deposition of accelerated In+ on clean Si(100)2x1 and Si3N. substrates in an MBE system equipped with an ultra-high vacuum (UHV) metal-ion source similar to that discussed in reference 14. The ion source provides beams in which up to 45 % of the total flux incident at the substrate can be: ionized and accelerated to energies between 50 and 500 eV. Figures 1a and 1b show scanning electron micrographs of the distribution of In on Si(lOO)2:x1 surfaces after the deposition of 200 monolayers (ML) at T, - 30 ·C. For thermal In deposition. a Stranski-Krastanov growth mechanism was observed in which the initially deposited In nucleated two-dimensionally and formed an InC2x!) overlayer with a maximum thickness of 3 ML. Higher In coverages resulted in the formation of <011> oriented polyhedral islands as shown in Figure 1a. This was explained by Knall et a1.  as being due to enhanced diffusion down channels in the dimerized (2x1) surface. The lateral growth rate of the islands was very low resulting in the formation of quasi-one-dimensional metal wires which covered only about 7% of the total surface area even after 200 ML of deposition.
In Island/Si(lOO) 2X1- In
Ts =70°c, Ei =Thermol, 8=200ML
T5 = 70°C, Ei =300eV. 8=200ML
Scanning electron micrographs of In islands deposited from (a) a thermal In beam and (b) a partially ionized 300 eV In+ beam on Si(lOO)2x1 surfaces at T. - 30 ·C. The total In coverage in each case was IIln - 200 ML. (From references 15 and 13. respectively).
Figure 1b shows the corresponding SEM micrograph for a film deposited upto the same coverage from a partially ionized 300 eV In beam.  Ion bombardment at T. - 30·C eliminated preferential formation along <011 > channels and resulted in the growth of more equiaxed islands. The nucleation rate (and hence the island number density) was much higher. the In islands covered a much larger surface area, and island coalescence was already apparent.
Barnett et a1.  have. for the first time. directly measured ion-irradiation-induced increases in adatom binding energies using a combination of modulated-beam mass spectrometry and thermally-stimulated desorption techniques. In these experiments. 1 ML of thermal Sb. was dissociatively chemisorbed on clean Si(l00) surfaces maintained at 425 ·C. The binding energy of thermal Sb at this coverage was determined to be 2.33 eV . However. Ar+ irradiation of 1- ML-Sb/Si samples with doses up to 2 X 1016 cm-z produced an additional "preferential" binding site at 2.6 eV due to recoil collisions. Although these experiments were carried out at higher ion energies than are normally used during film growth. the results demonstrate that such kinds of measurements are capable of providing the quantitative data necessary for modeling ion/surface effects during nucleation and the early stages of film growth.
Several authors [IS] have reported a decrease in dn/dt in the presence of ion irradiation leading to larger average island sizes D. for a given nominal film thickness. and hence larger ultimate grain sizes. Larger D values might be expected to occur under conditions (e.g .• high Jj• medium to high E1• and elevated Tstrm)* where the dominant ion bom.bardment effect is the depletion of small clusters by both sputtering and dissociation. Clusters of subcritical size are energetically unfavorable  and will dissociate into adatoms some of which will desorb or diffuse to feed larger stable islands. Figure 2 shows TEM micrographs of In islands deposited at 30 ·C (T,rrm - 0.7) on Si3N. in UHV . The total In flux in the partially-ionized beams was 4.6 x 1013 cm-2 s-1 and the ion-to-neutral flux ratio. Jj/J o- was 0.36. Increases in E, from thermal to 150. 200. and 300 eV resulted in a continuous increase in D from 6.5 to 8 to 13 to 50 nm for (nominally) 10 nm thick films. The secondary nucleation rate was also dramatically suppressed by ion irradiation as can be clearly observed by comparing the micrograph from the (nominally) 10- nm-thick layer grown from a purely thermal flux with that obtained from the layer grown with E, - 300 eV.
It should be noted that the dissociation of small clusters does not require a direct ion impact if the cluster is within the collision cascade region. l.e. within several lattice spacings. Ion irradiation can also act to directly (rather than indirectly as discussed above) increase adatom diffusivities by the initiation of shallow collision cascades and the excitation of surface phonons. However. the excess energy of incident accelerated ions. as well as the excess energy gained by adatoms involved in individual cascade collisions. will be lost to the lattice. i.e. the adatom becomes thermalized. within several vibrational periods. Thus this mechanism should not be expected to result in enhanced diffusion over distances of more than several lattice spacings.
In summary. it is clear that energetic particle bombardment can greatly affect nucleation and growth kinetics of polycrystalline films. and hence. as will be discussed in the next section. grain size. preferred orientation. and defect concentrations. However. much work remains to be done to understand these effects in detaiL Considerably less is known about the growth of epitaxial layers by accelerated beams.
Narusawa et aL  reported. several years ago. a decrease in the epitaxial temperature T, of MBE Si on S;(l11) and Alz03(1I02) by ionizing a small fraction of the evaporant flux and accelerating it to the substrate. T, was found to decrease by more than 100 ·C in both cases after ionizing ~ 1% of the incident Si flux and accelerating it to 200 and 100 e V. respectively. Beckers and co-workers [21.22] have developed a hot cathode discharge. high-energy (10-15 keY). UHV. mass-filtered ion beam system followed by a deceleration lens to provide accelerated beams of Ag" and Si" with currents of the order of 10 p.A at energies between - 20 and 100 eV. With this apparatus. they were able to grow epitaxial films of Ag on Si(l11) at room temperature using acceleration energies between 25 and 100 eV. Epitaxial Si layers were also grown on Ge(l00). Si(l00). and Si(ll!) at T. ~ 230·C using 50 eV sr-,
Possible mechanisms. other than "sputter cleaning." [23.24] for the ion-bombardment induced enhancement in film epitaxy can be visualized in molecular dynamics simulations of crystal growth such as those by Muller . Low-energy bombardment provides local atomic rearrangement allowing atoms to relax into lower energy sites. Obtaining reduced epitaxial temperatures requires a balance of the beneficial effects of ion irradiation such as "enhanced diffusion" while minimizing residual damage by continuously annealing out bombardment-induced defects during deposition. Thus. the most favorable deposition conditions would seem to be: high J,IJ. ratios. low Ej• and low deposition rates.
* T. and the melting point Tm are expressed in degrees K.
Bright field transrmssion electron micrographs of In islands on Si3N. substrates. Results are shown for two different nominal film thicknesses. t - 1.5 and 10 nm. The incident In beams were either thermal or partially ionized and accelerated to energies E; - 150 • 200. or 300 eV. The total In flux in the partially-ionized beams was 4.6 X lOll cm-2s-1 and the ionized fraction was 0.36. (From feference 13).
III. MICROSTRUcruRE EVOLUTION: DEFECf PRODUCfION AND ANNIHILATION
There is presently a growing interest in the use of low-energy ion irradiation to modify the microstructure. state of stress. defect concentration. and physical properties of as-deposited layers. Ion bombardment of films during deposition at low temperatures where irradiation-induced defects cannot be annealed out generally results in the mean stress becoming more compressive  (films grown using thermal beams at low T. are typically in tension). a reduction in the average grain size. and an increase in the dislocation density. "Low temperature" in this context is often defined as T.!fm < 0.3 . However. it should be noted that the T, range for obtaining a given microstructure can depend strongly on deposition parameters as well as otherfactors such as, for example, the substrate crystal structure and orientation . The development of in-plane compressive stress in irradiated films deposited at low temperatures is caused by both recoil implantation processes  and rare gas incorporation  depending upon the deposition conditions.
Huang et at.  have recently studied the effect of Ar+ ion bombardment during the growth of Ag films at T. - 2S-4S·C using a UHV dual-ion-beam apparatus. They showed that the use of average irradiation "energy densities" <E> ranging from thermal (obtained by evaporation) to 190 eV per deposited metal atom resulted in the grain size decreasing from 42 to 14.5 nm with the dislocation density increasing from 0.7 to 13.2 X lOll cm-2 as shown in Figure 3. In addition, the degree of (111) preferred orientation decreased while the plane stress reversed from 0.6 X 10" N m-2 tensile to a value of - 4.5 X 10" N m-2 compressive for <E> > 42 ~V. The optical properties of these films were found to be controlled by the void density which decreased with increasing <E> [32).
6o';-------~------~------,_------_16N' 'E u
I I I ,
I -j'--......o!l __ ----......o!l.-j4 c
00~--~5~0---~10~0~--~1~5~0---2-JOOO 0 Average Energy per Incident Atom, <E> (eV)
The grain size D and the dislocation density Nd in Ag films deposited at T, - 25-45 'C as a function of the average energy <E> per depositing atom. (Plotted from data given in reference 30).
The microstructure of films deposited from the vapor phase at low temperatures (or zone 1 in structure-zone models) [27.33.34] is composed of open columnar structures with extended voids along column boundaries. A typical example is shown in Figure 4 . The columns themselves are often not single grains but are composed of smaller more equiaxed grains. Computer simulations [36,37) have shown that the columnar structure is the result of low-adatom mobilities combined with 'self-shadowing" by previously quenched-in regions. The columnar structure is not only characteristic of polycrystalline films but also occurs in amorphous materials.
Scanning electron micrograph showing the microstructure of a Cr film deposited by cylindrical magnetron sputter deposition onto a glass substrate cooled by Iiquid nitrogen. (From reference 35).
The porous structure of columnar films generally results in poor mechanical and optical properties and the films are quite sensitive to the environment due to adsorption of water vapor and other atmospheric contaminants in the voids. Low-energy ion bombardment of the growing film has been used to interrupt the columnar structure. fill in the void network. and produce films with environmentally-stable refractive indices . If the defect density produced by the irradiation is sufficiently high. renucleation can occur. altering and sometimes completely eliminating the columnar structure .
Miiller [40.41] has recently used a Monte Carlo simulation of film growth to explain many of the effects described above. The deposition temperature was assumed to be low. such that adatom diffusivity was negligible. and. in the absence of ion bombardment. a columnar structure was obtained. In the presence of ion irradiation. however. sputtering of weakly bound material. ion incorporation. and recoil implantation acted to fill the void network. Important predictions of this model are that the film density should increase almost linearly with the ratio of the accelerated to thermal lhlXes JlI. and that there should be an optimum ion energy ~t for densification.
The above model has been verified in the case of CeOz films deposited by evaporating Ce in the presence of accelerated ot ions generated by a Kaufman-type ion gun. Figure 5 shows the agreement between the simulation and experimental measurements  of film density (the bulk density of Ce02 is 8.1 g cm-3) as a function of ion energy ~ for films deposited with J/J. - 1. Eit was found to be near 200 eV. For ~ < ~'. the number of recoils decreased while at larger Ei values an increasing fraction of the ion energy was lost deeper in the lattice. Extensions of computer simulations such as this should. in the future. also help to provide a better understanding of the relationship between ion bombardment and the development of stress in as-deposited films.
At higher deposition temperatures and low ~ values. defects which are produced in the nearsurface region due to low-energy irradiation are rapidly annealed out during film growth. The primary use of ion irradiation for microstructure modification in this T. range is to couple energy directly to the growth surface in order to. for example. decrease the bulk substrate temperature required for epitaxy as discussed in the previous section. Direct evidence that ion irradiation can result in a decreased defect density in as-deposited films has recently been obtained in experiments using transmission electron microscopy to investigate the dislocation density in single-crystal TiN layers grown by reactive magnetron sputtering in pure Nz on Mg0(100) substrates at T. between 550 and 900 ·C. Hultman et a1.  showed that the primary defects in the TiN films were dislocation loops whose number density Nd decreased with increasing T. for a given negative substrate bias V.. (In these experiments. the energy per incident accelerated nitrogen atom was - V;2 and J/J. was - 2). However. Nd decreased much more rapidly with increasing V, at constant T. until a minimum defect density was obtained at V. = v: after which Nd increased with further increases in V,.
jI /jV= 1
200 400 600
ION ENERGY Ei (eV) Experimental and theoretical values of the density p of Ce02 films deposited at ambient temperature by the simultaneous evaporation of Ce and ion beam acceleration of ot as a function of the ion energy E; for an accelerated to thermal fiux ratio ilia - 1. (From reference 42).
The major effect of ion irradiation in the TiN growth experiments was to enhance atomic mobilities thereby accelerating the rate at which defects were annealed out during deposition. Films grown at T. > 750 ·C and V. = V: were essentially free of dislocation loops. For comparfson, the dislocation Joop density in films grown with V. - 0 ranged from 5 X 10'2 to 1.5 X 1010 cm-2 as T, was increased from 550 to 850 ·C. This can be seen fairly dramatically in Figure 6 which shows TEM micrographs from films grown at 850 ·C with V, a 0 and SOO "C with V. - 400 V.
Vs = -400 V
Plan-view transmission electron micrographs of epitaxial TiN(l00) films grown at (a) T. - 850·C and V, = 0 and (b) T. = 800·C and V, - 400 V. (From reference 43).
IV. ELEMENTAL INCORPORATION PROBABILmES
Accelerated ions have been used to increase the incorporation probabilities U of both dopant and matrix species by several orders of magnitude and to decrease the amount of dopant surface segregation during deposition in order to provide better control over compositional depth distributions. An example of the use of accelerated ions to increase the incorporation probability of a matrix element is the growth of epitaxial TiN.(llO) on MgO by reactive magnetron sputtering . For a given N2/ Ar sputtering gas ratio and growth temperature. the concentration of N in the as-deposited film increased with increasing negative substrate bias due to collisional dissociation of N/. the dominant nitrogen ion in the discharge (the N2 binding energy is 9.7 eV) . and N implantation. Single-crystal TiN. layers with x between 0.6 and 1.0 (the full range of the mononitride equilibrium phase field)  were. obtained. In addition. metastable overstoichiometric single crystals. still in the B-1 NaCI structure. were grown' with Nrfi ratios up to 1.2 as shown in Figure 7 .
TiN (110) Ts = 700°C
I I I I
," 1.0 - • .:: ... ~ .. --~
o INz = 1
o INz =0.5
-100 -200 -300
Applied Substrate Bias, VB
NfTi ratio in epitaxial TiN.(llO) films as a function of the applied negative substrate potential V. during deposition on MgO by reactive magnetron sputtering. The total Ar + N2 sputtering pressure was 3 mTorr and the N2 fraction fN, was either 0.5 or 1. (From reference 45).
A common application of ion bombardment is to controllably modify. through preferential resputtering. the composition of alloys during growth, Examples include rf bias-sputter deposition of amorphous magnetic alloys such as Gd-Co and Gd-Co-Mo [471. Harper and Gambino  have modeled the preferential loss. due to resputtering by 500 eV Ar+ ions. of Gd from Gd-Co alloys deposited in a dual-ion-beam sputtering apparatus from GdCo. Gd~. and GdCo3 targets. Figure 8 shows the results (data points) plotted as film composition vs the total amount of material resputtered. The curves were obtained using best-fit values of the ratio E of the Gd-to-Co sputtering yields. E was found to be a strong function of film composition.
The primary interest in the use of accelerated dopant beams during vapor phase film growth is in microelectronics. Most of the common dopants used in both Si and GaAs device technology present problems during film growth by MBE due to low incorporation probabilities and/or pronounced surface segregation rendering control over both the bulk doping concentrations and depth distributions difficult for a wide range in growth conditions. Examples of systems with low o values include  As. Sb. In. and Ga in Si and Zn. Cd. Mn. S. and Te in GaAs. Systems exhibiting strong surface segregation include  Sb. In. Ga. and Al in Si and Sn. Pb. Te. Cr. and Mn in GaAs.
__ o •
____ .. --
0.8 ~:".t."--- •
~ . L --0---_0 __ -., <.::5
~ O.20c~ __ ::~-b. ... -_A_
it --o- __ -.:-===tC===~5
Measured fraction of Gd (open symbols) and Co (solid symbols) in deposited films vs the fraction of the film lost by resputtering. Data from three targets are shown: nominally GdCo (data represented by circles), GdC02 (triangles), and GdCo3 (squares). The lines show calculated atomic fractions of Gd (dashed lines) and Co (solid lines) for best-fit values of the sputter yield ratio E - 2.5, 4.5, and 5.0. (From reference 48).
Segregation gives rise to distorted profiles such as those shown in Figure 9 for two In-doped regions separated by a nominally-undoped buffer layer in MBE Si . The dotted lines show the expected depth profiles obtained, assuming no segregation, from known incorporation probabilities  for the growth conditions given in the figure. The actual measured profiles were determined by secondary ion mass spectrometry (SIMS) using ion-implanted standards. As film deposition commenced, the initially deposited dopant species segregated to the receeding growth surface leaving a dopant depleted region> 300 nm wide. A corresponding dopant accumulation layer, which at the end of the first doping layer yielded an In coverage 61n - 0.06 ML, - 4 orders of magnitude higher than the steady state In bulk concentration, formed at the growth surface of the film. This excess In at the surface then served as a reservoir for doping the succeeding "undoped" buffer layer. Similar results have been observed in other systems [52-54].
M BE st. In Ideal Profile -------
J :lx lOIScm-2 $-1 SIMS Profile "'"
5, 620.C 640.C Coleu loled -----
Ts:620"C4" rTs:6400C~ I f- ...... ~;;:
Ideal (dashed lines), experimentally determined (data points), and calculated (solid lines) depth profiles of the In concentration through a four-layer MBE Si film grown with a Si flux JSi = 1 X 1015 cm-2s-1. The growth conditions for each layer were: (1) T. - 640 ·C, Jln = 1 X 1011 cm-2s-'; (2) T. - 640 ·C, Jln - 0; (3) T, was decreased continuously from 640 to 620 ·C, Jln - 0; and (4) T, - 620 ·C and Jln = 1 X lOll cm-2s-'. (Taken from reference 50).
Recently. there has been a strong interest in the use of ionized and accelerated dopant beams to both increase tr and decrease the amount of surface segregation . The dopant incorporation model developed by the group at the University of Illinois [54.55] has been successfully applied to this case using additional terms. such as trapping. to account for ion/surface interactions. Some of the first experimental  (and calculated) (57] results are shown in Figure 10 for As+ in MBE Si. fTM for accelerated As with EM - 400 eV was increased by up to - 8 orders of magnitude over that observed for thermal species and electron mobilities equal to the best bulk Si:As values were obtained for T, > 750 ·C. Rockett et al.  have reported increases in <TIn of over 4 orders of magnitude using 100 eV In+ ions in MBE Si and have recently observed increases in fTln of 2 to 3 orders of magnitUde with EIn - 40 eV. The amount of segregation-induced profile broadening was greatly decreased leading to sharp In doping profiles as shown in Figure 11. Temperature dependent Hall mobilities in uniformly doped layers were equal to values reported for bulk Si:In samples .
o ..... ~.; . .::-e-~"'-
o .. ,
EAs(eV) Experiment Calculations
800 0 .............
600 Do ------
400 0 ---- Figure lU.
incorporation probability tr M of accelerated As+ ions in Si(100) during MBE growth as a function of temperature T, and ion energy EA,· (Data from reference 56. calculated results from reference 57).
Jorke et al. [60,61] have taken advantage of the strong surface segregation exhibited by Sb during the MBE growth of Si (9Sb is typically 0.2-1 ML) to increase fTSb by recoil implantation from the adlayer. In their experiments. they ionized and accelerated a fraction of the Si flux to energies between 100 and 1000 eV. Increases in fTSb of up to three orders of magnitude were obtained . In addition, the authors reported complete electrical activation of the dopant in films grown at T, - 650 "C with no degradation of carrier mobility .
The use of accelerated-ion doping during sputter deposition has also been investigated. In glow discharge bias-sputtering. the ion flux (primarily due to the discharge gas) incident at the growing film is typically of the same order of magnitude as the flux of depositing film species. Thus at low substrate biases (V,). the dominant effect of ion bombardment is generally to decrease tr due to loss by preferential sputtering. This tendency is exacerbated in the presence of strong surface segregation. However. as V, is increased. (J" reaches a minimum and finally begins to increase as trapping effects dominate sputtering. An example is S doping from H:zS in sputterdeposited single crystal GaAs films . Substrate bias has also been shown to lead to a reduction in the amount of segregation-induced profile broadening in Sri-doped GaAs films due to a comhination of preferential sputtering and recoil implantation.
l15rn SIMS Profile
is; = lxlOI5cm-2s-1
Doping profiles through four layers of a multilayer MBE Si(l00) film. The layers were grown at temperatures between 700 and 1200 ·C and doped with 100 eV accelerated In+ ions according to the schedule shown in the inset. (Taken from reference 58).
V. GROWTH OF SINGLE-CRYSTAL METASTABLE SEMICOllIDUcroR ALLOYS
An important application of ion/surface interactions during deposition is the growth of new metastable phases. In fact. techniques have recently been developed for the growth of a variety of new single-crystal thermodynamically-metastable semiconductors including [1,2] InSbl_.Bi., (GaAs)(l--x)(G~)., (GaSb)I_X(Ge2)., (GaSb)(I-x)(Sn2)X , and Gel-xSnx . A key feature in the growth of most of these alloy systems is the use of low-energy self-ion or inert-ion bombardment of the growing film. "Low-energy" in this context (typically - 10 to 200 eV for medium mass projectiles) refers to energies with a corresponding ion range of not more than a few lattice spacings. This provides continual collisional mixing of the upper one or two layers during deposition. Higher ion energies (Le, larger mean ion ranges) give rise to persistent effects such as enhanced diffusion in the condensed "bulk" lattice leading to phase separation. The ratio of the ion-to-thermal atom fluxes in these experiments is typically between 0.1 and 1.
Of particular interest have been the (IlI-V)(I-x)(IV2). alloys (GaAs\I--x)(Ge2)'  and (GaSb)I_X(Ge2).  for which epitaxial layers have been grown at compositions ranging across the pseudo binary phase diagrams of both systems even though the maximum Ill-V /IV solid solubilities are less than - 4 at. % . These alloys have been shown to exhibit good temporal and thermal stability due to the large kinetic barrier (- 3 eV in (GaSb)I_.(Ge2).) compared to the small thermodynamic driving force (- 30 meV) for phase separation . A combination of Raman spectroscopy [68,69], extended X-ray absorption fine structure.(EXAFS) , and high resolution triple-crystal X-ray diffraction  studies have been used to show that the atomic arrangement of (GaSb)I_.(Ge2). has perfect short range order (i.e. no III-III or V-V nearest neighbors) at all compositions but exhibits a long range zincblende-to-diamond structural transition at x.::: 0.3. Recent reviews on the growth and properties of metastable semiconductors may be found in references 1, 2, and 72.
It is clear from the discussion in Sections II through V that the use of low-energy ion/surface interactions during film growth from the vapor phase offers the crystal grower new opportunities for controllably altering film nucleation and growth kinetics and hence the microstructure, microchemistry, and physical properties of as-deposited layers. There is already a large body of
literature in this field and a number of practical applications in produ~tion. In addition •. it is clear that over the last several years there has been a significant increase m. our understandmg of the detailed mechanisms associated with ion/surface interactions and their ~ects on .fundamental growth processes. However. there are sti11large gaps in our knowledge. particularly I~ the role of ion/surface interactions in controlling nucleation kinetics. More fundamental r~ch IS necessary if the advantages inherent in the use of ion/surface interactions are to be fully exploited,
The authors gratefully acknowledge the Joint Services Electronics Program. the Materials Science Division of the Department of Energy. the Semiconductor Research Corporation. and the Swedish National Science Research Council (NFR) for sponsoring various phases of this research work.
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This paper also appears in Mat. Res. Soc. Symp. Proc. Vol 75
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