NITROGEN-ENABLED HIGH GROWTH RATES IN HYDRIDE VAPOR PHASE EPITAXY
20200407873 ยท 2020-12-31
Inventors
- Elisabeth Lynne MCCLURE (Lakewood, CO, US)
- Kevin Louis SCHULTE (Denver, CO, US)
- Aaron Joseph PTAK (Littleton, CO, US)
- John David SIMON (Austin, TX, US)
- Wondwosen Tilahun METAFERIA (Aurora, CO, US)
Cpc classification
C30B25/14
CHEMISTRY; METALLURGY
H01L21/0262
ELECTRICITY
C30B25/10
CHEMISTRY; METALLURGY
C30B25/08
CHEMISTRY; METALLURGY
International classification
C30B25/08
CHEMISTRY; METALLURGY
C30B25/14
CHEMISTRY; METALLURGY
Abstract
Disclosed herein are methods and devices that use a low-thermal conductivity inert gas to shield reactant gases and thus enabling a cold wall operation within a hot wall system.
Claims
1. A reactor capable of the deposition of at least one layer of a semiconductor device by using hydride vapor phase epitaxy (HVPE) using at least one group III metal source, at least one group V hydride gas, and an inert carrier gas, wherein the reactor comprises at least one source zone region at a temperature of up to about 800 C., and at least one deposition zone region at a temperature of below about 700 C.; and a delivery means to the deposition zone region wherein the delivery means comprises the inert gas carrier and reactant gases comprising a group III metal and at least one group V hydride gas that are flowed towards a growth substrate at a volumetric flow rate.
2. The reactor of claim 1 wherein the deposition zone region is below about 650 C.
3. The reactor of claim 1 wherein the at least one layer of the semiconductor device is GaAs.
4. The reactor of claim 3 wherein the GaAs deposition is up to 528 m/h.
5. The reactor of claim 1 wherein the rate of deposition of the at least one layer of a semiconductor device is improved by up to 32 percent when compared to using H.sub.2 as a carrier gas in the reactor instead of the inert carrier gas.
6. The reactor of claim 1 wherein the volumetric flow rate for the inert carrier gas and group V hydride gas is up to 5000 sccm.
7. The reactor of claim 1 wherein the volumetric flow rate for the group V hydride gas is up to 100 sccm.
8. The reactor of claim 1 wherein the partial pressure for the group V hydride gas within the inert gas carrier and reactant gases is up to 0.01 atm.
9. The reactor of claim 1 wherein the partial pressure for the gas comprising the group III metal within the inert gas carrier and reactant gases is up to 0.0012 atm.
10. A method for growing at least one layer of a semiconductor device using a reactor comprising at least one source zone and at least one deposition zone wherein the method comprises hydride vapor phase epitaxy (HVPE) using at least one group III metal, at least one group V hydride gas, and an inert carrier gas.
11. The method of claim 10 wherein the at least one source zone is at a temperature of up to about 800 C., and wherein the at least one deposition zone is at a temperature of up to about 700 C.
12. The method of claim 10 wherein the at least one layer of the semiconductor device is GaAs.
13. The method of claim 12 wherein the GaAs growth rate is up to 528 m/h.
14. The method of claim 10 wherein the growth rate of the at least one layer of a semiconductor device is improved by up to 32 percent when compared to using H.sub.2 as a carrier gas in the reactor instead of the inert gas.
15. The method of claim 10 wherein a volumetric flow rate of the inert carrier gas and group V hydride gas is up to 5000 sccm.
16. The method of claim 10 wherein a volumetric flow rate for the group V hydride gas is up to 100 sccm.
17. The method of claim 10 wherein a partial pressure for the group V hydride gas within the inert carrier gas is up to 0.01 atm.
18. The method of claim 12 wherein a surface roughness of the GaAs layer is below 0.8 nm.
19. The method of claim 12 wherein an electron mobility of the GaAs layer is up to 1600 cm.sup.2/V-s.
20. The method of claim 12 wherein an electron concentration of the GaAs layer is up to 9.910.sup.18 cm.sup.3.
Description
DESCRIPTION OF THE DRAWINGS
[0008] Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
[0009]
[0010]
[0011]
[0012]
[0013]
[0014]
[0015]
DETAILED DESCRIPTION
[0016] Disclosed herein are methods that use nitrogen as a carrier gas in HVPE. By using nitrogen as a carrier gas in HVPE, record fast growth rates reaching 432 microns/hour (about 40% faster than the current record using hydrogen as a carrier gas) have been observed.
[0017] The two largest cost barriers for III-V photovoltaics are those of both the growth and the substrate. Therefore, enhancing the growth rate of III-V semiconductors would increase the throughput of these devices, which decreases the total costs associated with growth with a simple modification to reactant gases. Additionally, use of a nitrogen ambient is potentially necessary to enable the nucleation and growth of GaAs epilayers on a monolayer-graphene coated GaAs substrate, because H.sub.2 is known to etch graphene at typical reactor temperatures. Remote-epitaxy through graphene and liftoff is a technology that is useful as a route to reduce substrate costs.
[0018] In an embodiment, disclosed herein are record GaAs growth rates approaching 530 m/h using nitrogen carrier gas and 400 m/h using hydrogen carrier gas in a dynamic-hydride vapor phase epitaxy reactor. Computational fluid dynamics modeling was performed to study the effect that either nitrogen or hydrogen carrier gas has on heat and mass transfer given the potential AsH.sub.3 decomposition at surfaces. As disclosed herein through experiments and support with modeling, nitrogen carrier gas enhances the growth rate compared to hydrogen carrier gas in a hydride-enhanced regime by minimizing the amount of arsine that decomposes before reaching the wafer surface.
[0019] Previous work using HVPE has demonstrated that using nitrogen as a carrier gas in HVPE slows the growth rate of III-V semiconductors. However, as disclosed herein, experiments using a dynamic-HVPE tool have resulted in a growth rate increase from 20%-100% when using nitrogen as a carrier gas instead of hydrogen, which indicates an exciting discovery contrary to conventional wisdom. Without being limited by theory, a hydride-enhanced growth mechanism does not require H.sub.2 to participate in the reaction, and H.sub.2 is potentially a product of the reaction AsH.sub.3+GaCl->GaAs+H.sub.2+HCl. This means that there are potential advantages to using an inert and/or higher density carrier gas, which thus makes the use of N.sub.2 enabling. A final advantage is that a nitrogen environment is non-flammable, which increases the safety of this growth technique compared to growth in a hydrogen ambient.
[0020] Previously, others in the art have stated that since argon and nitrogen are gases with heavier atomic weight, that the growth rate would be lower than that of hydrogen at the same temperature. However, as disclosed herein, the heavier gas can also affect the density and potentially thin the boundary layer thickness to enhance the growth rate. Without being limited by theory, hydrogen may be both a carrier gas and reactant that participates in the reaction to enhance the growth rate. Hydrogen may play a role in both the forward and reverse reactions.
[0021] Without being bound by theory, since the partial pressure of GaCl increases in nitrogen at the expense of HCl, solid GaAs tends to vaporize into the gas phase with the increase of the mole fraction of nitrogen and hence a reduction in growth rate is observed. However, the effect of partial pressure may be offset by the reduction in boundary layer thickness or difference in thermal conductivity between hydrogen and nitrogen.
[0022] Disclosed herein are methods and devices that use a low-thermal conductivity inert gas to shield the reactant gases and hence create a regime of cold wall operation within a hot wall system. In contrast to using a low thermal conductivity carrier gas that lowers the temperature of all of the reactant species, using methods and devices disclosed herein protects the stream of hot gases from the temperature of the reactor walls.
[0023] In another embodiment, disclosed herein is a method for the insulation of reactant gases by a low-thermal conductivity inert gas for hot wall vapor phase reactors. As disclosed herein, a heavy, inert gas with low thermal conductivity (such as nitrogen, argon, krypton, xenon, etc.) is flowed through an outer tube such that it surrounds reactant gases flowed through a central port towards a substrate in a hot wall vapor growth reactor. The reactant gases are insulated from the high temperatures of the reactor walls by the heavy outer gas, preventing their decomposition.
[0024] Growth in a hydrogen ambient at standard growth temperatures can either lead to arsine decomposition or, if gas velocity is increased to transport the reactants to the surface more quickly, reduce uniformity. Arsine can decompose into arsenic dimers and tetramers in a hot wall growth reactor at standard growth temperatures. However, it is advantageous to transport undecomposed arsine to the surface. High gas velocity can be used to transport arsine to the surface more quickly, in a hydride-enhanced growth mechanism. However, a high flow rate can lead to poor growth uniformity across a substrate, which impairs yield. Using an inert gas with low thermal conductivity flowed through an outer tube in order to encapsulate the arsine as it flows to the surface prevents decomposition without requiring exceedingly high reactant velocities or low pressures. A low-conductivity inert gas that blankets the reactant gases also eliminates the flammability risk of having a hydrogen ambient in a hot furnace.
[0025] As disclosed herein HVPE has demonstrated a hydride-enhanced regime in which a significant amount of uncracked AsH.sub.3 reaches the wafer surface, resulting in much higher growth rates due to the lower kinetic barrier to growth. In both the As.sub.x and the hydride-enhanced regime, the rate-limiting step to GaAs growth is the reduction of GaCl complexes that form on the surface. In the As.sub.x regime, GaCl can be removed either through reduction assisted by the H.sub.2 carrier gas to form HCl as a byproduct, or by a slower mechanism where three GaCl are converted to volatile GaCl.sub.3. Slower GaAs growth rates were historically observed with an inert carrier gas due to the slower reaction mechanism in the absence of H.sub.2. In contrast, the hydride-enhanced regime enables the direct reaction of AsH.sub.3 with GaCl to form GaAs without any influence of any carrier gas. The effect of inert carrier gas on growth rate has not been studied in the hydride-enhanced regime.
[0026] GaAs Growth Rates of 528 m/h Using D-HVPE with a Nitrogen Carrier Gas
[0027] Disclosed herein are experiments that confirm the observation of lower growth rates in the As.sub.x regime when using N.sub.2 as a carrier gas instead of H.sub.2, yet reveal a notable increase in growth rate when using N.sub.2 in the hydride-enhanced regime. Demonstrated herein are growth rates up to 528 m/h using N.sub.2 carrier gas, compared to 400 m/h using H.sub.2 carrier gas. CFD modeling was used to investigate the effect of carrier gas on internal reactor temperature and relative group V partial pressures to identify potential mechanism for these exceptional growth rates. Using methods disclosed herein, very similar material quality was achieved regardless of the growth regime used.
[0028] In an embodiment, materials were grown in a dual-chamber D-HVPE reactor. In an embodiment, a simplified schematic of the reactor can be found in K. L. Schulte, et al., High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides, Applied Physics Letters, vol. 112, p. 042101, 2018; and U.S. Pat. No. 9,824,890 by D. L. Young, et al., entitled High throughput semiconductor deposition system. In an embodiment, GaCl and InCl were formed in-situ by the reaction of anhydrous HCl over elemental Ga and In for the group III sources. Hydride gases were used for the group V source, and n-type doping was achieved using hydrogen selenide (H.sub.2Se). The gas plumbing design is such that the carrier gas species is either H.sub.2 or N.sub.2, but not a combination of both. Changes in the AsH.sub.3 carrier flow (Q.sub.N.sub.
[0029] The modeling was performed with the commercially available computational fluid dynamics package CFD-ACE+, which allows the user to build and define the geometry in which reactions take place, set initial boundary conditions, and detail the composition and flow of the desired reactants. In an embodiment of the modeling experiments, the temperature was fixed at the reactor walls in the simulation to values of 800 C. at the source zone and 650 C. in the deposition zone, as it is in the real reactor. The effective rate constant for the decomposition of arsine at those temperatures were manually input into CFD-ACE+ from values previously reported in order to take into account AsH.sub.3 cracking into As.sub.4. The model assumes that any AsH.sub.3 that reaches the surface will react with available GaCl to deposit GaAs, an assumption which seems to align well with experimental results. The 3D geometry used for these simulations was a single growth chamber, where carrier gas flows through either a center tube as the carrier for AsH.sub.3 or through an inlet that approximates the flows through the actual top port and source boats.
[0030] It has been demonstrated that a higher Q.sub.H.sub.
[0031] The data shown in
[0032] CFD modeling was also used to better understand the influence of the carrier gas on the extent of AsH.sub.3 decomposition. In these simulations, carrier gas flows through either a center tube to simulate Q.sub.N.sub.
[0033]
[0034]
GaCl+AsH.sub.3GaAs+HCl+H.sub.2(1)
[0035] and the growth rate increases with enhanced preservation of AsH.sub.3. Without being bound by theory, because GaAs has a lower kinetic barrier to growth under AsH.sub.3 than As.sub.x, and less AsH.sub.3 decomposition occurs with the low thermal conductivity carrier gas, the resulting growth rate is higher for N.sub.2 compared to H.sub.2.
[0036] For low Q.sub.N.sub.
GaCl+ As.sub.4+H.sub.2GaAs+HCl(2)
[0037] is the reaction attributed to GaAs growth. In this case, H.sub.2 participates as a reactant and enables higher growth rates compared to GaAs growth with N.sub.2. This explains both the decrease in growth rate observed in
3GaCl+As.sub.42GaAs+GaCl.sub.3(3)
[0038] where the carrier gas plays no direct role in the reaction. For disproportionately large amounts of group III precursors, this reaction mechanism can yield higher GaAs growth rates compared to H.sub.2. However, for the GaCl partial pressure of 0.0012 atm used in these experiments, it is statistically improbable to assemble 3 GaCl molecules to create GaCl.sub.3, leading to the observed lower growth rate with N.sub.2 due to these kinetic limitations. Together,
[0039] The average surface roughness, electron mobility, electron concentration of the samples in
[0040] The electron mobility and concentration were determined using Hall-effect measurements of GaAs epilayers grown with the same H.sub.2Se flow between samples. The electron mobilities are high at all growth rates using H.sub.2 carrier gas, and only begin to degrade by 300 cm.sup.2/V-s between 483 m/h and 389 m/h with N.sub.2 carrier gas. Additionally, the value of electron mobilities are reasonably close between H.sub.2 and N.sub.2 carrier gas, which is a promising result for device quality at high growth rates with N.sub.2 since excellent device performance has been realized with H.sub.2.
TABLE-US-00001 TABLE 1 Average surface roughness, electron mobility, and electron concentration for the samples in FIG. 4 for a range of growth rates using N.sub.2 or H.sub.2 carrier gas. Average Electron Growth rate roughness Mobility concentration (m/h) Carrier gas (nm) (10.sup.3 cm.sup.2/V-s) (10.sup.18 cm.sup.3) 33 N.sub.2 0.35 1.6 2.1 213 N.sub.2 0.26 1.0 9.9 320 N.sub.2 0.36 1.2 7.6 389 N.sub.2 0.30 1.2 7.0 483 N.sub.2 0.38 0.9 4.5 528 N.sub.2 In progress 23 H.sub.2 0.78 1.4 2.5 167 H.sub.2 0.36 1.0 5.3 216 H.sub.2 0.29 1.1 7.4 264 H.sub.2 0.26 1.2 6.8 336 H.sub.2 0.37 1.3 4.7 400 H.sub.2 In progress
[0041] Using methods and devices disclosed herein, record growth rates up to 400 m/h using H.sub.2 and 528 m/h using N.sub.2 in a D-HVPE reactor have been demonstrated, with smooth surfaces and high electron mobility demonstrated up to growth rates of 336 m/h and 483 m/h for the respective carrier gases. The high throughput, lower cost, and safety benefits of the N.sub.2 compared to the incumbent H.sub.2 used in III-V As/P HVPE systems make N.sub.2 an attractive alternative for carrier gas. CFD modeling showed that enhanced AsH.sub.3 delivery to the wafer surface enabled by a lower internal reactor temperature using a N.sub.2, whereas more As.sub.x reaches the wafer surface with H.sub.2. However, for low AsH.sub.3 carrier gas flows, significant AsH.sub.3 decomposition occurs, and As.sub.x becomes the predominant group V reactant. In this case, H.sub.2 plays an enabling role in the growth mechanism, and subsequently a higher growth rate is observed with H.sub.2 instead of N.sub.2. This result indicates that it is possible to grow GaAs at high growth rates under a N.sub.2 environment which should reduce deposition cost by eliminating expenses associated with producing and handling H.sub.2 in a high temperature environment.