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In this paper, we report on deposition and properties of nanocrystalline Ge:H films . The films were grown from germane and hydrogen mixtures using Radio frequency Plasma-enhanced chemical vapor deposition (RF-PECVD) process using ∼45 MHz frequency. The crystallinity of the films was measured using Raman measurements and from x-ray diffraction techniques, it was found that the grain size was a strong function of deposition pressure, temperature and hydrogen/germane ratios. High hydrogen ratios and high powers led to films with smaller grains. Higher pressures and smaller hydrogen/germane ratio led to films with larger grain sizes, as did higher growth temperatures. The mobility of electrons and holes was measured using space charge limited current (SCLC) techniques in n+-n-n+ devices. It was found that nominally undoped films were generally n type with carrier concentrations in the 1E14/cm3 range. Mobility was found to increase with grain size, with 60 nm grains showing mobility in the 2-3 cm2/V-s range.

A one-dimensional model has been developed for radio frequency (RF) glow discharge of SiH4/GeH4/H2 3-gases mixture at a high pressure regime based on the fluid model. The behavior of electrons, neutrals, radicals and ions with corresponding rate constants is described by driftdiffusion equations that are coupled with the Poisson’s equation and solved with an explicit central-difference discretization scheme. The germanium (Ge) content in the deposited film and germane (GeH4) radical fraction in the gas phase are found to decrease as total gas pressure increases in contrast to the increased deposition rate, which are explained by the fact that GeHx-group species are more thoroughly depleted and less promoted by the denser plasma at high pressure compared to SiHx-group species. The multiplied population of electrons and hydrogen atoms in the quadratically denser plasma also boosts secondary reactions which are favorable for SiH3 and GeH3 and consume SiH2 and GeH2for high order radicals.

Chemical annealing is a powerful technique for controlling H bonding and optical absorption in amorphous semiconductors. We have shown previously that the use of careful chemical annealing by Argon can lower the bandgap of a-Si:H while maintaining electronic properties in both films and devices. In this work, we describe new work on chemical annealing of A-(Si,Ge):H films and devices. The technique consists in growing very thin layers (1-3 nm) of A-(Si,Ge) from mixtures of hydrogen, Silane and Germane, and then subjecting this thin layer to ion bombardment by Ar. The cycle is repeated many times to achieve the desired thickness of the intrinsic layer. The resulting film and device were measured for their composition using energy dispersive spectroscopy (EDS) analysis. We discovered that the composition itself, namely the Ge:Si ratio in the film, could be varied by changing the ion bombardment conditions. Lower energy bombardment led to a higher Ge:Si ratio for the same germane/Silane ratio in the gas phase. By controlling ion bombardment during the Ar annealing cycle, we were able to reduce the H content of the film and achieve good electronic properties. It will be shown that by appropriate control over ion energies, one can obtain films and devices which are of good quality and low bandgap as well.

Boron (B) doping of plasma deposited silicon films have been widely studied and applied in many devices, while B-doping of germanium has been poorly reported in literature. We have reported previously about Ge:H films with low density of localized states deposited by LF plasma with optimal hydrogen dilution.This work is devoted to a study of boron incorporation and its effect on electronic properties in Ge:H films. The films were obtained by low frequency (LF) plasma deposition from GeH4+SiH4 +B2H6 mixture diluted with hydrogen. The deposition parameters were as follow: substrate temperature Ts = 300 oC, discharge frequency f= 110 kHz, pressure P= 0.6 Torr, power W= 300 W, germane flow QGeH4= 50 sccm, silane flow, hydrogen flow QH2=3500 sccm, diborane flow was varied in the range of QB2H6=0 to 20 sccm providing boron concentration in gas phase in the range of Y=0 to 4%. Composition of the films was characterized by SIMS profiling. Hydrogen bonding was studied by FTIR. Temperature dependence of conductivity measured in DC regime in vacuum thermostat was employed to study carrier transport. Optical measurements provided optical gap, sub-gap absorption and refraction index. Boron incorporation in solid film demonstrated fast increase in the range of Y = 0 to 1.4% and then increase became slower. Hydrogen concentration in the films was determined by absorption of Ge-H stretching mode at k ≈ 1870 cm−1 and it showed weak increase with change of Y from 0 to 4%. Activation energy of conductivity increased in the range of Y = 0 to 1.5% suggesting a compensation of electron conductivity, reaching maximum value Ea =0.5 eV (corresponding approximately to Eg/2) at Y= 1.5%. Then Ea reduced to minimum value Ea = 0.27 eV at Y= 3.5% showing a trend to saturation with further Y increase. This behavior is related to change of charge transport from electron to intrinsic at Y= 1.5% and further to hole transport.

We report on a systematical study of growth rate, surface morphology, hydrogen and oxygen incorporation, optical and electrical properties in Ge:H and GeYSi1-Y:H, Y> 0.85 films, deposited in a capacitive reactor by low frequency PE CVD. Silane and germane were used as feed gases diluted by hydrogen. Hydrogen dilution characterized by R= QH2/[QSiH4+QGeH4], where QH2, QSiH4, and QGeH4 are gas flows of hydrogen, silane and germane, respectively. The flow was varied in the range of R=20 to 80. Composition of the films was characterized by SIMS profiling. We did not observed a significant change of the deposition rate Vd in GeYSi1-Y:H films in all the range of R, while for Ge:H films Vd was significantly reduced after R=50. AFM characterization of the surface morphology demonstrated that at R=50 average height (R) reached maximum in both Ge:H and GeYSi1-Y:H films, while average diameter (R) had a minimum in GeYSi1-Y:H films and maximum in Ge:H films. Both Ge:H and GeYSi1-Y:H films demonstrated change of E04 in the studied range of R, and a minimum clearly appeared in E at R=50-60 suggesting significant reduction in weak bonds of these films. The activation energy of conductivity Ea slightly increases with R in Ge:H films and shows no definitive trend in GeYSi1-Y:H: films. Both FTIR and SIMS data show a general trend of reducing hydrogen and oxygen content with R. These two types of films showed different behavior and correlations between surface morphology and optical and electrical properties.

Demand for integration of optoelectronic functionality (e.g., optical interconnects) with silicon complementary metal oxide semiconductor (CMOS) technology has for many years motivated the investigation of low temperature (∼ 450°C) germanium deposition processes that may be integrated in to the back-end CMOS process flow. A common challenge to improving the germanium quality is the thermal budget of the in-situ bake, which is used to reduce defect forming oxygen and carbon surface residues. Typical cleaning temperatures to remove significant concentrations of oxygen and carbon have been reported to be approximately 750°C for thermal hydrogen bakes in standard chemical vapor deposition chambers. Germanium device performance using lower peak in-situ cleans (i.e., ∼450°C) has been hampered by additional crystal defectivity, although epitaxy is possible with out complete removal of oxygen and carbon at lower temperatures.Plasma enhanced chemical vapor deposition (PECVD) is used to reduce the processing temperature. Hydrogen plasma assisted in-situ surface preparation of epitaxy has been shown to reduce both carbon and oxygen concentrations and enable epitaxial growth at temperatures as low as ∼150°C. The hydrogen is believed to help produce volatile Si-O and H2O species in the removal of oxygen, although typically this is not reported to occur rapidly enough to completely clear the surface of all oxygen until ∼550°C. In this paper, we describe the use of an in-situ argon/germane high density plasma to help initiate germanium epitaxy on silicon using a peak temperature of approximately 460°C. Germanium is believed to readily break Si-O bonds to form more volatile Ge-O, therefore, argon/germane plasmas offer the potential to reduce the necessary in-situ clean temperature while obtaining similar results as hydrogen in-situ cleans. To the authors knowledge this report is also the first demonstration of germanium epitaxy on silicon using this commercially available high density plasma chamber configuration instead of, for example, remote or electron cyclotron resonance configurations.

The morphology of Si1-Y GeY:H films in the range of Y=0.23 to 0.9 has been studied by AFM. The films were deposited by Low Frequency (LF) PE CVD at substrate temperature Ts=300 C and discharge frequency f=110 kHz from silane+germane mixture with and without, Ar and H2 dilution. The films were deposited on silicon and glass substrates. AFM images were taken and analyzed for 2x2 μm2 area. All the images demonstrated “grain” like structure, which was characterized by the height distribution function F(H) average roughness , standard height deviation Rq, lateral correlation length Lc, area distribution function F(s), mean grain area , diameter distribution function F(d), and mean grain diameter . The roughness of the films monotonically increases with Y for all dilutions, but more significantly in the films deposited without dilution. Lc continuously grows with Y in the films deposited without dilution, while more complex behavior of Lc(Y) is observed in the films deposited with H- or Ar dilution. The sharpness of F(H) characterized by curtosis γ depends on dilution, and the sharpest F(H) are for the films deposited with Ar ( γ=5.30,Y=0.23) and without dilution (γ=4.3, Y=0.45). Isothermal annealing caused an increase of , Lc in the films deposited with H- and Ar dilutions, while in the films prepared without dilution the behavior was more complex, depending on the substrates. After the annealing a significant sharpening of the height distributions, F(H), was observed in the films deposited with H dilution or without dilution.

Nanocrystalline Ge and its alloys with C are potentially useful materials for solar cells, thin film transistors and image sensors. In this paper, we discuss the growth and properties of these materials using remote, low pressure ECR plasma deposition. The materials and devices were grown from mixtures of germane, methane and hydrogen. It was found that high hydrogen dilutions (>40:1) were needed to crystallize the films. Studies of x-ray spectra revealed that the grains were primarily oriented. The grain size was a strong function of hydrogen dilution and growth temperature. Higher growth temperatures resulted in larger grain size. High hydrogen dilution tended to reduce grain size. These results can be explained by recognizing that excessive amounts of bonded H can inhibit the growth of grain, which is the thermodynamically favorable direction for grain growth. Grain sizes as large as 80 nm were obtained in nc-Ge. Addition of C reduced the crystallinity. Mobility and carrier concentrations in nc-Ge were measured using Hall effect. Mobility values of ˜5cm2/V-sand carrier concentrations of ˜1x1016/cm3were obtained in larger grains. p+nn+ devices were fabricated on stainless steel substrates and compared with similar devices deposited in nc-Si:H. It was found that the voltage decreased and current increased in nc-Ge devices, in comparison with devices in nc-Si:H. Addition of C to Ge devices increased the open circuit voltage and shifted the quantum efficiency to larger photon energies, as expected.

Hydrogenated amorphous silicon (a-Si:H) solar cells incorporating high deposition rate (8-10Å/s) intrinsic layers were deposited using modified very high frequency (MVHF) plasma. We have monitored the light scattered from powder generated in the plasma using an Ar-laser and a silicon photodiode. This simple, non-invasive technique allows us to make measurements on the same reactor used to make the solar cells. First, we have varied the total flow rate and observed a maximum in the scattered light intensity from powder in the plasma during the deposition of the intrinsic layer, and correlated this with the degradation, as well as the stabilized performance of the solar cells. Then, we have studied the effects of varying the deposition temperature and/or the addition of germane to the gas mixture on the scattered light intensity due to powder in the plasma.

In this paper, we investigate the chemical vapor deposition (CVD) of Ge nanocrystals (NCs) directly on hafnium oxide HfO2 dielectric for non-volatile memory applications. Germane GeH4 was used as a precursor. Atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were used to characterize the Ge NCs. The dependence of the Ge NC size and density on the deposition temperature, deposition time, and flow rate was explored. A high Ge NC density of 1011 cm-2 was obtained at a deposition temperature of 600°C, with a mean diameter of about 16 nm. MOS capacitors with CVD Ge NCs embedded in the HfO2 gate dielectric were fabricated. Hysteresis of capacitance-voltage (C-V) characteristics of capacitors with Ge NCs was observed, demonstrating memory effect.

We have found that narrow-bandgap—1.25 < Tauc Gap < 1.50 eV—amorphous silicon germanium (a-SiGe:H) alloys grown by hot-wire chemical vapor deposition (hot-wire CVD) can be improved by lowering both substrate and filament temperatures. We systematically study films deposited using a one-tungsten filament, decreasing filament temperature (Tf) from our standard temperature of 2150° down to 1750°C, and fixing all other deposition parameters. By decreasing Tfat the fixed substrate temperature (Ts) of 180°C, the Ge-H bonding increases, whereas the Si-H2bonding is eliminated. Films with higher Ge-H bonding and less Si-H2have improved photoconductivity. For the series of films deposited using the same germane gas fraction at 35%, the energy where the optical absorption is 1x104(E04) drops from 1.54 to 1.41 eV with decreasing Tf. This is mainly due to the combination of an increasing Ge solid fraction (x) in the film, and an improved homogeneity and compactness due to significant reduction of microvoids, which was confirmed by small angle X-ray scattering (SAXS). We also studied a series of films grown by decreasing the Tsfrom our previous standard temperature of 350°C down to 125°C, fixing all other deposition parameters including Tfat 1800°C. By decreasing Ts, both the total hydrogen content (CH) and the Ge-H bonding increased, but the Si-H2bonding is not measurable in the Tsrange of 180°-300°C. The E04 increases from 1.40 to 1.51 eV as Tsdecreased from 350° to 125°C, mainly due to the increased total hydrogen content (CH). At the same time, the photo-to-dark conductivity ratio increases almost three orders of magnitude over this range of Ts.

The structural and electrical properties of boron doped amorphous silicon-germanium alloy films, obtained using a low frequency plasma enhanced chemical vapor deposition (LF PECVD), are presented in this contribution. These thin films were deposited on a substrate heated at 270°C, and by decomposing a mixture of silane, germane, and diborane gases. The chemical bond structure was studied by Infrared Spectroscopy. Our results show that, for a constant diborane flow, the increase of germane flow enhances the incorporation of boron into the film; the peak at 2540 cm−1 becomes larger as the Ge content increases. Transport of carriers was studied by measuring current-voltage curves as a function of temperature. The conductivity increased from 10−6 to 10 (Ω-cm)−1, while the refraction index increased from 3.312 to 4.4458, for an increasing Ge content; this makes the films suitable for optical waveguide applications. On the other hand, the activation energy varied from 0.668 to 0.220 eV when the sample was doped with boron. The AFM images showed that the surface roughness was improved for an alloy with 50% of Ge.

Nanocrystalline Germanium-Carbon alloys, denoted by nc- (Ge,C):H, are a potentially useful new electronic material whose bandgap can be varied by changing the Ge:C ratios. We have shown previously that nanocrystalline (Ge,C):H films can be grown using remote ECR plasma deposition. In this paper, we report on the crystal structure, electron mobility and some device related properties of these materials. The materials were grown using mixtures of either Germane and methane, with significant hydrogen dilution, or from mixtures of ethylene and germane, also with significant hydrogen dilution. X-ray diffraction measurements indicated a predominantly crystal structure. The grain size was in the range of 10 nm. Raman measurements clearly show the 300 cm-1 Ge peak in the films. Electron Hall mobilities were measured in these films and were found to be in the range of 2.5-3 cm2/V-sec. Proof-of-concept p+nn+ junction devices were fabricated and showed distinct photovoltaic properties. The open circuit voltage was found to be a strong function of the itnerfaces between n+ and n layers, and between p+ and n layers. The use of an amorphous n+/n interface at the back of the improved the device performance significantly. Capacitance measurements indicated that the device behaved according to standard p/n junction theory, with the n- doping in the base layer being in the 1017/cm3 range. Thus, the base layer was not intrinsic, but rather n type, as may be expected for a crystalline as opposed to amorphous material. Quantum efficiency data indicated that as C was added to the material, the edge of the QE curve shifted to higher photon energies, indicating larger bandgaps.

Nanocrystalline germanium thin-films deposited on glass by plasma-enhanced chemical vapor deposition from germane and hydrogen were doped with phosphorus and boron. We report some electrical transport and structural properties of Ge films as a function of dopant species and doping levels. The dark conductivities of the phosphorus- and boron-doped films are approximately three to four orders of magnitude higher than the intrinsic nanocrystalline germanium. In the solid phase, phosphorus comprised about 1 atomic percent in the Ge bulk over the range of source gas ratios used, and the conductivity remained fairly constant, indicating saturated conditions. Boron comprised about 10 atomic percent in Ge at the highest dark conductivity, while increased doping turned the films amorphous. To test the doped layers for device applications, an all-nanocrystalline germanium p-i-n diode was constructed and showed rectification when measured in the dark at room temperature.

We report on the growth and properties of amorphous Silicon-Germanium [a–(Si,Ge):H] films and devices fabricated at growth rates of ∼ 5 Å/sec using a remote ECR plasma growth process. The films and devices were made using mixtures of germane and silane along with dilution with hydrogen and helium. The addition of He to the gas mixture significantly increased the growth rates. It was found that hydrogen was always necessary in order to achieve the best film and device properties. Films and devices were made across the entire bandgap range, from a-Si to a-Ge. High ratios of photo/dark conductivity and low values of Urbach energy ( > 50 meV) indicate good film properties. The defect densities were measured using space charge limited current techniques. The defect densities were in the range of 1-2 x 10 16/cm 3 –eV, about 5 times higher than for a-Si:H. Electron mobility-lifetime products were measured and found to be in the range of 2-4 x 10-7 cm2/V, even for low gap materials (1.35 eV). Single and graded gap devices were fabricated in these materials. Device fill factors of ∼ 70% were obtained in graded gap devices.

When Ge is deposited epitaxially on Si, the strain energy from the lattice mismatch causes the Ge in layers thicker than about four monolayers to form distinctive, three-dimensional islands. The shape of the islands is determined by the energies of the surface facets, facet edges, and interfaces. When phosphorus is added during the deposition, the surface energies change, modifying the island shapes and sizes, as well as the deposition process. When phosphine is introduced to the germane/hydrogen ambient during Ge deposition, the deposition rate decreases because of competitive adsorption. The steady-state deposition rate is not reached for thin layers. The deposited, doped layers contain three different island shapes, as do undoped layers; however, the island size for each shape is smaller for the doped layers than for the corresponding undoped layers. The intermediate-size islands are the most significant; the intermediate-size doped islands are of the same family as the undoped, multifaceted “dome” structures, but are considerably smaller. The largest doped islands appear to be related to the defective “superdomes” discussed for undoped islands. The distribution between the different island shapes depends on the phosphine partial pressure. At higher partial pressures, the smaller structures are absent. Phosphorus appears to act as a mild surfactant, suppressing small islands.

Germanium films deposited on glass by plasma-enhanced chemical vapor deposition from germane and hydrogen grow in the structure succession of amorphous-nanocrystallineamorphous-nanocrystalline as the substrate temperature is raised from 30°C to 310°C. We ascribe the phase formation, from low to high temperature, to a sequence of low to high mobility of Ge growth species on a surface that is hydrogenated at low temperature but not hydrogenated at high temperature. We report some structural, optical, and electrical transport properties of Ge films as a function of deposition temperature and film thickness.

We report on the growth and electrical and optical properties of micro- and poly- crystalline Ge1−x Cxfilms. This is a new material which does not exist in nature. The films were grown using ECR plasma techniques under conditions of low pressure and high power from a mixture of germane, methane and hydrogen. The bandgap of the material could be varied from that of c-Ge (∼0.7 eV) to almost 1.15 eV by changing the methane/germane ratio. X ray diffraction and Raman measurements indicated good crystallinity in the film. The optical absorption spectrum of the film resembles that of c-Ge, with a near direct bandgap, implying that as C is added, both the central and the L valley in the conduction band move up simultaneously, while maintaining a small (∼0.15 eV) separation between the two. The Hall mobility was measured to be 70 cm2/V-sec. The films were doped n- type using phosphine, and p- type using diborane. P-n junctions with good rectification characteristics were fabricated. Because of its excellent optical absorption, this material may be suitable for photovoltaic applications, particularly for tandem junction cells. We have also observed that grain size can be controlled using H etching, and have observed distinct changes in optical properties related to quantum size effects in c-Ge films.

For sensor applications in the detection of near infrared light we have prepared μc-Ge:H by plasma enhanced chemical vapor deposition (PECVD) with a mixture of germane and hydrogen, investigatedits structural and electronic properties and incorporated it into thin pin diodes. In order to ensure microcrystalline growth we had to use high hydrogen dilution. However, only the material prepared with a ratio of germane to hydrogen of 0.2% shows high crystallinity. The optical absorption is remarkably different from c-Ge and exhibits no indication of a direct gap at 0.8eV. When this material is implemented as part of a 110nm thin absorber, a short circuit current of 20mA/cm2 and a quantum efficiency of 15% at a wavelength of 1.1μm are achieved. Higher germane concentrations in hydrogen lead to poor electronic properties due to an increase of the amorphous phase and the short circuit current of the devices deteriorates. As for crystalline germanium photodiodes cooling of the devices is used to overcome the restrictionoriginating from the high free carrier concentration.

Plasma deposition using silane and germane is extensively used for depositing amorphous (Si,Ge) films and devices, and has the potential of also being used for making crystalline films. In this paper, we report results on the electrical and optical characterization of germane plasmas using a Langmuir probe set-up and optical emission spectroscopy. The plasma studied was an electron-cyclotron-resonance plasma. For the first time ever, we have detected the characteristic 246 nm GeH emission peak in the plasma. The GeH emission peak is suppressed significantly when small quantities of hydrogen are added as a diluent gas. We have also studied the effect of adding a voltage bias to the substrate on the plasma properties. We find that adding voltage bias does not simply change the effective ion energy impinging on the substrate, as is usually assumed, but also changes all the plasma properties, including the density of neutral, excited H radicals arriving at the growing surface.

We report on the growth and fabrication of low-gap a-(Si,Ge) solar cells, including cells made from a-Ge:H. The cells were deposited from silane and germane, or germane alone, using a high dilution of hydrogen in a remote ECR plasma reactor. We have been able to achieve a Tauc gap of as low as 1.15 eV with good device properties. The fill factors were in the 50%-60% range, and the Urbach energies measured in devices were in the range of 45 meV. The devices were of the p/i/n type with light entering the p layer. The devices were fabricated on stainless steel substrates. We also report on experiments to improve graded gap solar cells in a- (Si,Ge) using a novel combination of ppm-boron dopant and bandgap grading. It is shown that this grading significantly improves the device performance, both voltage and fill factor.

We report on the growth of microcrystalline Si and (Si,Ge) cells on stainless steel substrates. The devices were grown using a remote, low pressure, ECR growth technique at low temperatures (250-350 C). The precursor gases were silane, germane and hydrogen. The devices were of the p-i-n type, with light incident on the p layer. The p layer was a-(Si,C). A novel interface buffer layer, consisting of an amorphous alloy whose bandgap was graded from 1.3 eV to 1.9 eV was used to match the crystalline base layer with the higher gap p layer. It was found that the properties of this buffer layer were critical in determining the properties of the resulting device. The buffer layer was found to increase the voltage by almost 20%. Cells with high fill factors were made using this technique. The quantum efficiency data indicated that the base layers had absorption characteristic of crystalline materials.

A-SiGe n-i-p solar cells with i-layer deposited via plasma enhanced chemical vapor deposition (PECVD) with a germane to disilane ratio of 0.72 and hydrogen dilution R=(H2 flow)/(GeH4+Si2H6 flow) values of 1.7, 10, 30, 50, 120, 180 and 240 were deposited on stainless steel substrates. This germane to disilane ratio is what we typically use for the i-layer in the bottom cell of our standard triple-junction solar cells. Solar cell current-voltage curves (J-V) and quantum efficiency (QE) were measured for these devices. Light soaking tests were performed for these devices under 1 sun light intensity at 50° C. While device with R=30 showed the highest initial efficiency, the device with R=120 exhibit higher stabilized efficiency after 1000 hours of light soaking.Single-layer a-SiGe films (∼500 nm thick) were deposited under the same conditions as the i-layer of these devices on a variety of substrates including 7059 glass, crystalline silicon, and stainless steel for visible-IR transmission spectroscopy, FTIR, and hydrogen effusion studies. It is interesting to note 1) the H content in the film decreased with increasing R based on both the IR and H effusion measurements, and 2) while the H content changes significantly with different R, the change in Eg is relatively small. This is most likely due to a change in Ge content in the film for different R.

Microcrystalline silicon germanium alloys (ν-Si1−xGex:H) exhibit an enhanced optical absorption in the near infrared region with increasing germanium content. Therefore, the employment of this material as intrinsic absorber is a promising challenge for thin film technology in photovoltaics and sensorics. The influence of hydrogen dilution on the material and the performance of pin diodes prepared in a PECVD process with 10 % GeH4 in the gas phase is discussed. These results are compared with the characteristics of diodes prepared with higher germane content in the gas phase. With increasing germane content the solar cell parameters Voc and FF decrease and the deposition regime where good optoelectronic properties are observed is narrowed.

We successfully grow high-quality hydrogenated amorphous-silicon-germanium alloys (a-SiGe:H) by the hot-wire chemical-vapor deposition (HWCVD) technique using silane and germane gas mixtures. These alloys display electronic properties as good as those grown by the plasma-enhanced chemical-vapor deposition (PECVD) technique, when comparing materials with the same optical bandgaps. However, we grow materials with good electrical properties at high deposition rates—up to 40 Å/s, compared to 1–4 Å/s for PECVD materials. Our alloys exhibit similar trends with increasing Ge content to alloys grown by PECVD. The defect density, the dark conductivity, and the degree of nanostructural heterogeneity (as measured by small-angle X-ray scattering) all increase with increasing germanium content in the alloy. The nanostructural heterogeneity displays a sharp transition between 9 at.% and 14 at.% germanium. PECVD- grown a-SiGe:H alloys exhibit a similar transition at 20 at.% Ge. The photoconductivity and the ambipolar diffusion length of the alloys decrease with increasing germanium content. For a fixed silane-to-germane gas ratio, all material properties improve substantially when increasing substrate temperature (Tsub) from 220°C to 375°C. Increasing Tsub also narrows the optical bandgap and lowers the hydrogen content in the alloys for the same germane-to-silane gas ratio.

In this work we explore how various growth characteristics of Ge on Si(001) can be used to fabricate structures for potential nanodevices. In the first example, the self-assembling tendency of germanium for three-dimensional islanding on Si(001) is considered, e.g. for application in devices based on quantum dots and wires. We aimed at achieving a detailed understanding of dot nucleation and growth mechanisms from germane. By controlling the deposition parameters, such as the germane pressure and substrate temperature, arrays of dots and antidots can be created on the grown surface, and further modified by post-deposition anneals. While lower temperature deposition leads to randomly distributed dots (i.e. small and coherent three-dimensional clusters with pyramidal shapes), a higher temperature deposition results in formation of antidots (i.e. pyramidal pits), which, in turn, are gradually replaced by the clusters, if the deposition is allowed to continue. The difference is caused by the different hydrogen behaviour at the respective temperature ranges. The germanium tendency to incorporate preferentially at the step and island edges is another beneficial property, which can be used to align the dots along step edges, creating wires rather than dots, or to fabricate ultrasmall Si-Ge heterojunctions, of a less than 10 nanometer size.

This paper reports on the growth and characterization of micro-crystalline (Si,Ge) films deposited on glass and polyimide substrates. The films were grown using a hydrogen diluted remote ECR plasma process. The feedstock gases were silane and germane. The entire range of composition from 100% Si to 100% Ge was studied. A low-pressure, low-substrate temperature, and high-power environment was used to change the morphology from amorphous to micro-crystalline. The films deposited at 5 mT pressure are generally micro-crystalline. The film's structure was studied using Raman spectroscopy. Raman spectra show clear, sharp crystalline-type Si and Ge peaks. Electronic properties of the films, such as activation energy and absorption constant down to α = 1 cm−1 were also measured. The sub-gap absorption data also show crystalline absorption behavior, with the absorption shifting to lower energies as the Ge content is increased. This absorption data shows that the materials have low defect densities.

Si / Si1-x-yGexCy / Si heterostructures containing up to 17 at.% Ge and 1.9 at.% C were grown on (001) silicon by low pressure Rapid Thermal Chemical Vapor Deposition, using a mixture of silane, germane and methylsilane, diluted in hydrogen. The samples were then annealed in a Rapid Thermal Processing furnace, under an atmospheric pressure of nitrogen, at temperatures ranging from 900 to 1130 °C.The samples were characterized using infrared spectroscopy and x-ray diffraction. SIMS profiling and TEM observation were performed on some of the samples.Substitutional C gradually disappeared, either precipitating out to form cubic silicon carbide (β-SiC), or simply vanishing into interstitial positions. In any case, the in-plane lattice constant remained constant after annealing, indicating that there was no mechanical strain relaxation by formation of misfit dislocations. The perpendicular lattice constant increased due to the decrease in substitutional C concentration, as well as it decreased due to the germanium out-diffusion. This variation of the strain during annealing was modeled, and allowed the determination of the kinetics of the substitutional carbon disappearance. The same behavior was observed for all samples. Indeed, the Cs disappearance rate was always increased for samples with higher initial Ge and C concentrations. The kinetics of this precipitation was found in very good agreement with previous published results.

Deposition of amorphous germanium by anodic PCVD was performed changing the germane/hydrogen dilution ratio from 1/6 to 1/100. Films deposited under high dilution of germane are of a high mechanical density (92.5 % of bulk) and good optoelectronic properties (electrical conductivity at room temperature σ=10−5 (Ω cm)−1, majority carrier mobility-lifetime product at λ=1200 nm ημ=x 10−7 cm2/V). The quality of the films is increased by deposition at increasing pumping speed for hydrogen (lower hydrogen pressure) keeping the other parameters constant. It is suggested that fast atomic hydrogen originating from a backscattering process at the powered electrode bombard the growing film and contribute to the improved quality of the a-Ge:H. Also, the growth kinetics of the films is changed from linear to parabolic dependence on germane flow interchanging deposition from high to low hydrogen pressure. This effect is rationalized in terms of a contribution of energetic atomic hydrogen to the dissociation of germane.

We have prepared hydrogenated macrocrystalline silicon germanium by plasma enhanced CVD of a mixture of silane and germane gas diluted with hydrogen. The growth conditions have been systematically controlled to obtain large (∼400Å) crystallites of silicon-germanium as observed using Raman scattering and x-ray diffraction. The dangling bond (germanium) density has been reduced to 16 cm−3 at low substrate temperatures (∼150°C). The optical absorption spectra of the 50% Ge containing material is red-shifted compared to microcrystalline silicon, consistent with a reduction of the indirect optical gap to 0.9eV. Schottky type cells fabricated using Au on an n+ crystalline silicon substrate confirm that the long wavelength response is remarkably enhanced in this material.

Device-quality epi material can be grown at temperatures ranging from 600 to 800°C in commercially available production reactors. The exceptionally steep transitions of Ge, B and, to a lesser extent, P, are characteristics of Si and strained SiGe epi growth from dichlorosilane and germane in hydrogen ambient at atmospheric or reduced pressure. Although the growth rates depend on the dopant gas flows at low temperatures, layer thickness and doping level control is excellent. Selective multilayer growth at reduced pressure seems a viable process and can be applied in e.g. HBT's.In spite of the fact that a lot of the progress in low-temperature epitaxy has been made in lampheated reactors, it is argued that RTP is not needed for low-temperature epitaxy. This is in contrast to conventional (high-temperature) epitaxy where RTP is becoming indispensable. Real RTP, heating and cooling the wafer in just a couple of seconds, would improve the throughput of the present generation single wafer epi reactors tremendously and seems feasible.

The defect-free band-edge photoluminescence at both 30K and 77K was observed for the first time in Si/SiGeC/Si quantum wells. The SiGeC samples were prepared by rapid thermal chemical vapor deposition (RTCVD) by using methylsilane as carbon source added in a dichlorosilane and germane mixture. Deep photoluminescence around 0.8 eV, previously reported by Boucaud et al., was no longer observed under any excitation conditions. Compared to control Si/SiGe/Si quantum wells, the initial effect of adding the C is to decrease the bandgap of the host SiGe layers, despite the fact that the diamond has a large bandgap.

Time resolved mass spectrometry and the measurement of appearance potentials of various GeH -cationic fragments combined with selfconsistent theoretical modelling have been used to study the mechanism of plasma induced deposition of germanium. It is shown, that the high rate deposition occurs via germylene, GeH as the direct precursor. Digermane May play some role only at low deposition rates. Although we could reproduce the best values of theμτ product reported so far, no further improvement could be achieved.

Computational programs are often used for estimating molecular orbital energies and geometries. The results of these calculations can also provide information needed for investigation of adsorption and decomposition mechanisms on surfaces. In this study, ab initio methods are used to calculate properties of gas phase diethylgermane and GeHx-substituted silanes (x=1−3). The silanes are used as models for surface Ge hydrides. The calculated gas phase molecular orbital energies are then compared with experimentally determined molecular orbital energies for the adsorbed species. The surface species are prepared by germane, digermane, ethylbromide, or diethylgermane adsorption on the Si(100)-(2×1) surface and the molecular orbital energies are measured by photoelectron spectroscopy.

We compare films of a-Ge:H deposited by plasma enhanced chemical vapor deposition (PECVD) using GeFLi diluted with H2, He and Ar. The nominal deposition conditions used were those which have produced high quality a-Ge:H with H2 dilution. Using H2 and He as diluents, three studies were done in which the parameters of substrate temperature, diluent gas flow and electrode gap spacing were independently varied. The photoelectronic properties of the films made with He dilution were quite good, although never better than those made with H2 dilution. The overall results indicated that for our nominal conditions hydrogen plays an important and crucial role in producing high quality films, and we believe that this role is mainly to reduce the probability of germane radical incorporation. In contrast to He and H2 dilution, dilution with Ar produced films with much poorer microstructure and a photoresponse two orders of magnitude lower. We attribute this to polymerization of the germane radicals which led to observed dust particles and a reduction in ion bombardment of the growing film.

Applying the previously derived “Three-Partial-Rates” model, CVD-Si/Ge-thin film growth and composition is described as influenced by the partial pressures of silane, germane, and hydrogen chloride. The effect of hydrogen carrier gas throughput variation is considered, as well as the density reduction of polycrystalline growth defects by the action of hydrogen chloride and hydrogen.

We have studied the deposition of GexSi1−x layers on (100) Si substrates by gas source molecular beam epitaxy (GSMBE) using disilane and germane.The investigation of RHEED intensity oscillations during growth reveals the well known rate enhancement obtained when adding a small amount of germane to the disilane flux. However, when exposing a previously deposited Ge layer to a pure disilane flux the growth rate during the first few monolayers remains at an enhanced value but returns to its homoepitaxial value after about 10 to 15 monolayers. This behaviour was observed under a variety of growth conditions. It is in marked contrast to the experience obtained in conventional Si/Ge MBE and suggests a catalytic effect of the particular surface present during GSMBE growth. We propose that this effect is caused by the surface segregation of Ge species and leads to a smear-out of the Ge profile in the layer.

We have studied methods of improving glow-discharge-deposited a-Si1−x Gex :H alloys deposited using silane and germane gas mixtures. Material processing methods studied include (1) varying the substrate temperature from 170° to 280°C, (2) varying the process gas composition and pressure, (3) dilution of the feed gas by hydrogen, argon, or helium, (4) enhancing etching during deposition by adding small amounts of XeF2 vapor into the process gas, and (5) postdeposition annealing and/or hydrogenation.

Dichlorosilanc and germane were used to grow silicon-germanium alloys at temperatures as low as 550°C at atmospheric pressure. Germanium mole fractions as high as 44% were obtained and the layers exhibit smooth surface morphology. Silicon-gcrmanium/silicon multilayers with abrupt hctero-intcrfaccs have been achieved. Cross Section Transmission Electron Microscopy, (XTEM) and High Resolution X-Ray Diffraction, (HRXRD) characterization of the hetero-interface abruptness will be presented. Recent results on two-dimensional (2-D) hole mobility structures grown by this technique will also be reported. Selective growth of silicon-germanium on oxide patterned silicon wafers was also demonstrated. A significant feature of the selective deposition is the lack of faceting at the oxide sidcwall, which has been commonly observed in high temperature silicon growth.

The disorder in a-Ge:H thin films produced by the plasma-enhanced chemical vapor deposition (PECVD) technique is strongly reduced when the GeH4 gas is diluted at 1% in H2 and the radiofrequency power density is increased to 0.1 W.cm−2. This improvement is attributed to a better surface passivation by the hydrogen atoms during the growth. However, the poor transport properties indicate a still high defect density. The midgap defect absorption and the Urbach energy, obtained from the photothermal deflection spectra calibrated with optical data, both decrease as a function of the film thickness. The optical defect density is calibrated with EPR spin measurements. For a-Ge:H films thicker than 2 μm, obtained at a deposition temperature Ts ranging from 150 to 250°C, the Urbach tail parameter E° is lower than 50 meV and not sensitive to Ts ; the dangling bond density is around 4.107 cm−3, which is higher by a factor of 100 than in a-Si:H. Preliminary transport measurements indicate that the Fermi level density of states is larger than 1018 cm−3.eV−1.

Undoped epitaxial layers of GexSi1−x have been grown on (100) silicon substrates using the UHV/CVD technique. Epitaxial films were obtained at growth temperatures between 577 and 665 C. The growth rate and germanium content of the layers has been determined as a function of the germane flow and the deposition temperature. A bake at 800 C was found to be highly beneficial in reducing the defect density and improving the film roughness.

Growth of SiGe alloys on GaAs substrates at temperatures as low as 590 °C is described. The growth has been accomplished using the pyrolysis of disilane (Si2H6) and Germane (GeH4) at such temperatures. The layers were characterized electrically and show n-type conduction with a carrier concentration of ~ 1 × 1018 cm−3. The high quality of the SiGe layers are evident in the Rutherford backscattering (RBS) channeling results on SiGe/GaAs structures. A Xmin of 5.6% has been obtained for a Si0.05Ge0 95 layer on GaAs. Xmin increases with increasing silicon content in the SiGe layers. The SiGe alloy layers were studied by x-ray diffraction, and the composition was determined assuming coherent, but tetragonally-distorted growth of SiGe on GaAs. The distortion calculations, based on theoretical elastic-constants, were confirmed using Auger electron spectroscopy to check alloy composition.

Growth of Ge on GaAs at reasonably high temperatures, which produce better crystallinity in the Ge, presents serious difficulties due to the dissociation of the GaAs substrate. In this paper, we describe the growth of a lowtemperature buffer layer of Ge on GaAs that prevents decomposition of the GaAs during high-temperature growth of Ge. Using this approach, we present the first report of highly specular, mass-transport-limited high-temperature growth of Ge on GaAs that is comparable to the homoepitaxy of Ge. The factors affecting the minority-carrier lifetime of Ge on GaAs, using such an epitaxial growth technique, were studied with a non-invasive microwave technique. Lifetime variations, from very low values to about 0.45 μsec, were obtained as a function of the growth conditions. Significantly, the removal of the surface oxide on the GaAs substrate prior to low-temperature buffer-layer growth, terminating the flow of germane(GeH4) during the ramp to high growth temperatures, thinner buffer layers, and high-temperature growth of Ge were found to be important for obtaining long lifetimes.

Selective depositions of germanium thin films have been investigated in a cold-wall, lamp heated rapid thermal processor. Films were deposited at low pressures (1 Torr-8 Torr) using the thermal decomposition of germane. Selectivity was maintained throughout the temperature range investigated, 350°C-600°C. Growth rates as high as 800 Å/min were obtained at 425°C where deposition is controlled by the surface reactions, making germanium compatible with the throughput requirements of single wafer manufacturing. Three dimensional growth was seen at temperatures above 450°C resulting in a rough surface morphology. Smooth films were deposited below 450°C with the films characterized by two dimensional growth. In this work, germanium is considered as a potential material to fabricate MOS transistors with raised source and drain junctions (UPMOS). Kelvin structures were fabricated to study the effect of the intermediate germanium layer between aluminum and silicon on contact resistance. It is shown that contact resistivity is improved by approximately 17% using an Al/p-Ge/p+-Si structure. In this work, it is also shown that titanium germanide formation can be used as a means of reducing the resistivity of the Ge buffer layer.

We have investigated the growth rate and boron doping of Sil-xGex epitaxial films grown by Limited Reaction Processing The growth experiments were carried out at a pressure of 6.0 torr with growth temperatures ranging from 625°C to 1000°C. The growth rate increases rapidly upon the additon of a small germane flow to the dichlorosilane in the reaction-rate-limited growth regime, and can not be explained simply by germanium incorporation. The presence of germane can increase the silicon growth rate by up to a factor of one hundred. Boron doping was also studied at high concentrations of boron in Si and Sil-xGex epitaxial films as a function of diborane flow and growth rate supports a simple kinetic model rather than an equilibrium model.

This paper discusses the bonding of hydrogen in a—Si,Ge:H alloy films prepared byreactive magnetron sputtering (RMS). We compare our results for H atom bonding with films produced by: (a) the glow discharge decomposition (GDD) of silane and germane mixtures, and (b) reactive diode sputtering (RDS). We discuss the energy states associated with Si and Ge atom nfeutrat angling bonds in the context of an empirical tight—binding modeL The model places the Ge atom dangling bond state deeper in the gap than the corresponding Si atom defect state. The differences between the electronic properties of GDDand RDS films, and R4S films are explained in terms of the degree of H compensation of Si and Ge atom dangling bonds.

a-S1−xCx:H and a-Si1− Ge :H films are prepared by magnetron sputtering in an argon-hydrogen-methane/germane atmosphere. The hydrogen content of the carbon alloy increases with x, saturating near 40 at% for the maximum C-content (x = 0.88). From a detailed analysis of the infrared absorption modes we conclude that the formation of (CHm)n C/Si-groups (n = 1,2,3, m = 2,3) is responsible for the growth of hy r gen rich and inhomogeneous films. Structural, electrical and optical properties of the films show characteristic changes near an alloy composition of x = 0.5 which indicate the transition to a structure with threefold coordinated carbon. For the germanium alloy system lower DOS and improved photoelectrical properties have been measured for y ≤ 0.01. Decreasing H-content and SiH2 /GeH2 bonding configurations impair the alloy properties for higher y.

The spatial and energetic characteristics of rf and dc parallel-plate deposition discharges are discussed, along with their implications to plasma chemistry. We discuss the results and interpretation of our recent measurements of silane, disilane, germane, and mixed-gas stochiometry. These yield the initial dissociation branching between even and odd dangling-bond radicals, as well as the relative roles of higher silanes and silyl germanes (produced by the discharge) in the chemistry. Our deposition model and supporting data are discussed, as are various causes of film-quality variations which this suggests.

High quality, low defect density, single crystalline silicon/germanium alloys have been grown on Si(100) substrate wafers in a low temperature UHV-CVD reactor. Using a silane/germane gaseous source, the growth rate of the epitaxial layer increases from 4 angstroms/minute with no germane present to 82 angstroms/minute with 12.7% germane present in the reaction gas mixture at 550C. The germanium/silicon ratio in the deposited alloy is a factor of two greater than the germane/silane ratio in the reaction gas mixture. The kinetics of this effect are studied and correlation to UHV hydrogen thermal desorption from single crystal silicon-germanium alloys are made.