CN103117209A - Gradient AlGaN layer preparation method and device prepared by same - Google Patents

Gradient AlGaN layer preparation method and device prepared by same Download PDF

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CN103117209A
CN103117209A CN2013100401892A CN201310040189A CN103117209A CN 103117209 A CN103117209 A CN 103117209A CN 2013100401892 A CN2013100401892 A CN 2013100401892A CN 201310040189 A CN201310040189 A CN 201310040189A CN 103117209 A CN103117209 A CN 103117209A
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algan layer
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张佰君
杨亿斌
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Sun Yat Sen University
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Abstract

The invention relates to the technical field of semiconductors, in particular to a gradient AlGaN layer preparation method and a device prepared by the same. When a gradient AlGaN layer is grown, flow of trimethylaluminum fed into a reaction chamber is gradually decreased, and flow of trimethylgallium is increased gradually. The function of the trimethylaluminum flow satisfies yTMAl=a-bx<m> or yTMAl=a(1-x)<m>+b, the function of the trimethylgallium flow satisfies yTMGa=cx<n>+d or yTMGa=c-d(1-x)<n>, x refers to normalization time of growing of the gradient AlGaN layer, and m and n are 1 asynchronously. By the aid of the different flow functions, change rates of TMAl and TMGa in different flows are changed, so that distribution of aluminum in the gradient AlGaN layer can be controlled effectively, further stress and crystalline quality of a GaN film growing on the gradient AlGaN layer are regulated and controlled, and a thick GaN film high in crystalline quality and free of crazing is grown.

Description

A kind of preparation method of gradual change AlGaN layer and the device that adopts the method to obtain
Technical field
The present invention relates to technical field of semiconductors, more specifically, relate to a kind of preparation method of gradual change AlGaN layer and the device that adopts the method to obtain.
Background technology
GaN has the characteristics such as large direct band gap (3.4 eV), high heat conductance, high electronics saturation drift velocity and large disruptive critical voltage, has therefore become the study hotspot of present technical field of semiconductors.III-nitride GaN, AlN(energy gap 6.2 eV), InN(energy gap 0.7eV) and the energy gap of the alloy that forms covered energy range from infrared to visible light, ultraviolet light, therefore have a wide range of applications at optoelectronic areas, as large power white light LED, ultraviolet, blue laser, the day blind detector of ultraviolet band, high-frequency high-power device etc.
Because large scale GaN crystal growth is very difficult, this makes isoepitaxial growth be difficult to extensive realization.Now be mainly way growing GaN film and the device on the backing materials such as sapphire, SiC that adopts heteroepitaxial growth.At present grow GaN material and the photoelectric device of better quality on these two kinds of substrates, realized the commercialization of product.But these two kinds of substrates are expensive, especially SiC.And the size of these two kinds of substrates is all smaller, has increased the cost of manufacture of device.In addition, Sapphire Substrate also has extreme hardness, conducts electricity the characteristics such as poor, poor heat conductivity, and is unfavorable to making and the performance of device.The advantages such as Si has low price as the most ripe present semi-conducting material, and size is large, and crystal mass is high, the capacity of heat transmission is good can reduce the cost of manufacture of chip greatly as epitaxial substrate with Si, improve business efficiency.
Yet have larger thermal mismatching between GaN and Si, the thermal mismatching degree is up to 56%, and this makes in the process of cooling after growth finishes, the GaN film can be subject to the larger tensile stress of Si substrate and chap, warpage, cause being used for the making of device.In addition, GaN and Si also exist larger lattice mismatch, and the lattice fit is 17%, and this makes the higher dislocation density of appearance in the GaN film, has reduced crystal mass.
But, stress is only the upper topmost problem of growing GaN of Si.In order to alleviate tensile stress, introduce and press gravitation, at present the main methods such as AlN resilient coating, AlN/GaN superlattice layer, ladder gradual change AlGaN layer and content gradually variational AlGaN layer that adopt.
Content gradually variational AlGaN layer is the comparison effective method.Can utilize like this difference of AlN and GaN lattice constant to form compression in growth course, part makes up the tensile stress that forms in temperature-fall period, thereby effectively reduces dislocation and crack density in epitaxial loayer.The component of the transition zone between everybody wishes from AlN to GaN is linear gradient, so all adopted the method for linear flow to realize the variation of al composition.Generally, to realize like this al composition gradual change in the AlGaN layer: be all in growth course at growth components gradual change AlGaN layer, pass into linear minimizing of trimethyl aluminium (TMAl) flow of reative cell, the linear increase of trimethyl gallium (TMGa) flow realizes.Yet this method can only grow the gradual change AlGaN layer that single al composition distributes, and can't regulate the distribution of its al composition, and stress and the dislocation density that also just can't effectively regulate the GaN film affect the crystal mass of GaN film.
In addition, due to TMAl and NH 3Have strong pre-reaction, this makes the AlGaN of high aluminium component be difficult to growth, and growth rate is very slow.Therefore, if be the flow linear change of TMAl and TMGa, can cause the AlGaN thinner thickness of high aluminium component, and the AlGaN thickness of low al composition is thicker, so in gradual change AlGaN layer, the distribution of al composition is not linear distribution as anticipation.So also can affect the crystal mass of GaN film.
Similarly, the defective that exists in above-mentioned AlGaN growth exists on SiC substrate and Sapphire Substrate equally, and principle is similar, if therefore can regulate the distribution of gradual change AlGaN layer Al component on SiC substrate and Sapphire Substrate, can optimize equally the crystal mass of GaN film.
Summary of the invention
The technical problem that the present invention solves is to overcome the deficiencies in the prior art, the preparation method of the controlled gradual change AlGaN layer of a kind of component distribution and the device that adopts the method to obtain are provided, and then can realize effectively regulating the stress of the GaN film of growing on gradual change AlGaN layer and the purpose of crystal mass.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of preparation method of gradual change AlGaN layer is before growth gradual change AlGaN layer, at first at Grown one deck AlN resilient coating; The method of growth gradual change AlGaN layer is: pass into NH in reative cell 3, trimethyl aluminium and trimethyl gallium, the trimethyl aluminium flow that wherein passes into reduces gradually, TMGa flow rate increases gradually;
The function of trimethyl aluminium flow is:
Figure 2013100401892100002DEST_PATH_IMAGE001
The function of TMGa flow rate is:
Figure 547796DEST_PATH_IMAGE002
Wherein, x is the normalization time of gradual change AlGaN layer growth, and m, n are not 1 simultaneously.
The present invention is in the process of growth gradual change AlGaN layer, the variation pattern that passes into trimethyl aluminium (TMAl) flow of reative cell and trimethyl gallium (TMGa) flow is the function (function of two flows is not linear function simultaneously) about the time, utilize different functions, can change TMAl and the TMGa rate of change when different flow.Thereby method of the present invention can realize effectively controlling the distribution of al composition in gradual change AlGaN layer, the distribution that realizes al composition is controlled, and then regulate and control on it stress and the crystal mass of the GaN film of growth, the thick GaN film that grows high-crystal quality and do not chap.
Further, the growing method of described gradual change AlGaN layer is Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, chemical beam epitaxy method or hydride vapour phase epitaxy method.
Further, described gradual change AlGaN layer growth temperature is 900 ~ 1100 ℃, and growth pressure is 50 ~ 200 mbar, and the V/III ratio is 500 ~ 4000.For temperature: if temperature is too low, can't grown crystal quality monocrystalline gradual change preferably AlGaN layer; If excess Temperature can reduce growth rate, add the load of large equipment.For growth pressure: if growth pressure is too low, can strengthen machine utilization, and can increase the edge dislocation of epitaxial film; If growth pressure is too high, can increase TMAl and NH 3Pre-reaction, the waste raw material simultaneously may cause the AlGaN of high component to grow.For the V/III ratio, too lowly can increase the epitaxial film edge dislocation, make rough surface; Too highly can increase TMAl and NH 3Pre-reaction, the waste source material.For thickness: if thickness is too little, can't alleviate tensile stress, be difficult to the thicker GaN film that does not chap of growing; If too thick, its compression that provides can be tending towards saturated, is even run through dislocation and discharges a part, causes the waste of material and the increase of cost.
Further, described gradual change AlGaN layer thickness is 0.8 ~ 2 μ m.
Further, the range of flow of described trimethyl aluminium is 400 ~ 0sccm, and the range of flow of trimethyl gallium is 0 ~ 200 sccm, best, work as NH 3During for 3000sccm, the range of flow of described trimethyl aluminium is 100 ~ 5sccm, and the range of flow of described trimethyl gallium is 3 ~ 15 sccm.Due to the control precision of mass flow controller (MFC), so the minimum of its flow is difficult to accurate control near 0, so the minimum value of flow is more slightly bigger than 0.
Further, the growing method of described AlN resilient coating is Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, chemical beam epitaxy method or hydride vapour phase epitaxy method.The thickness range of described AlN resilient coating is 50 ~ 300nm.
Further, described substrate is Si substrate, SiC substrate or Sapphire Substrate.
The device that a kind of preparation method who adopts above-mentioned gradual change AlGaN layer obtains comprises substrate, AlN resilient coating and gradual change AlGaN layer from the bottom up successively.
Compared with prior art, the beneficial effect of technical solution of the present invention is: the preparation method of a kind of gradual change AlGaN of the present invention layer, in the process of growth gradual change AlGaN layer, the variation pattern that passes into trimethyl aluminium (TMAl) flow of reative cell and trimethyl gallium (TMGa) flow is the function (function of two flows is not linear function simultaneously) about the time, utilize different functions, can change TMAl and the TMGa rate of change when different flow.Thereby the present invention can realize effectively controlling the distribution of al composition in gradual change AlGaN layer, realizes that the distribution of al composition is controlled, and then regulates and controls stress and the crystal mass of the GaN film of growth on it, the thick GaN film that grows high-crystal quality and do not chap.
Description of drawings
Fig. 1 is the structural representation of epitaxial growth GaN film on the gradual change AlGaN layer that obtains of the preparation method of the embodiment of the present invention.
Fig. 2 is the function relation figure of the changes in flow rate of the TMAl of three embodiment of the present invention and prior art and TMGa.
Fig. 3 is the curve that 2 θ ~ ω scans of the XRD of three embodiment of the present invention and prior art.
The SIMS test result schematic diagram that Fig. 4 provides for the embodiment of the present invention 1 and embodiment 2.
Fig. 5 is the Raman test result schematic diagram of the suffered biaxial stress of GaN film of three embodiment of the present invention and prior art.
Fig. 6 is the halfwidth of the XRD swing curve of three embodiment of the present invention and prior art.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is described further.The description of embodiment part just is used for schematically explanation the present invention, is not construed as limiting the invention.
For the ease of explaining and explanation, the size of various piece or structure does not represent actual size, have to exaggerate, and has to dwindle, and what accompanying drawing represented is only schematic diagram, but not pictorial diagram.Specifically describe for clear, some known function or structure may be the abridged, and the explanation of these structures has also been omitted.
Embodiment 1
The gradual change AlGaN layer preparation method of the embodiment of the present invention comprises the steps:
S1. grow one deck high temperature AlN layer 2 as resilient coating on Si substrate 1;
S2. growth one deck gradual change AlGaN layer 3 on high temperature AlN layer 2.
After gradual change AlGaN layer prepares, just can be on gradual change AlGaN layer 3 growing GaN film 4 and other required material layers successively, obtain needed device.
As shown in Figure 1, for the device architecture schematic diagram that obtains of epitaxial growth GaN film again on the gradual change AlGaN layer that obtains at said method, comprise successively from the bottom up Si substrate 1, high temperature AlN layer 2, gradual change AlGaN layer 3 and GaN film 4.
Wherein, the thickness of gradual change AlGaN layer 3 is 1 μ m, and growth temperature is 990 ℃, and growth pressure is 100 mbar, and the V/III ratio is 2000.Certainly the thickness of gradual change AlGaN layer 3 can be also a lot of the one-tenth-value thickness 1/10s such as 0.8 μ m, 1.2 μ m, 1.5 μ m or 2 μ m, if thickness is less than 0.8 μ m, do not have the purpose that improves the GaN film quality of growth on it, if thickness excessive (namely greater than 2 μ m) has increased device cost.Growth temperature, growth pressure, V/III can adjust according to the AlGaN film thickness that will grow or other needs than, wherein growth temperature range is 900 ~ 1100 ℃, the growth pressure scope is 50 ~ 200 mbar, and V/III is 500 ~ 4000 than scope.
The growing method of gradual change AlGaN layer 3 and high temperature AlN layer 2 is Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, chemical beam epitaxy method or hydride vapour phase epitaxy method.
Wherein in step S2, the method for growth gradual change AlGaN layer is: pass into NH in reative cell 3, trimethyl aluminium and trimethyl gallium, the trimethyl aluminium flow that wherein passes into reduces gradually, TMGa flow rate increases gradually.
As shown in Figure 2, the TMAl flow in the gradual change AlGaN layer of embodiment 1 drops to 5 sccm from 100 sccm, and its function is A=95 (1- x) 2+ 5 (sccm), the TMGa flow is raised to 15 sccm from 3 sccm linearities, and its function curve is G=12 x+ 3 (sccm).In above-mentioned function x(0≤ x≤ 1) for the normalization time of gradual change AlGaN layer growth.
Embodiment 2
The present embodiment is similar to Example 1, distinguishes only to be, the function of TMAl and TMGa flow is different from embodiment 1, is specially: in gradual change AlGaN layer growth process, the TMAl flow drops to 5 sccm from 100 sccm, and its function is B=100-95 x 2(sccm), the TMGa flow is raised to 15 sccm from 3 sccm linearities, and its function curve is G=12 x+ 3 (sccm).In above-mentioned function x(0≤ x≤ 1) for the normalization time of gradual change AlGaN layer growth.Function curve as shown in Figure 2.
Embodiment 3
The present embodiment is similar to Example 1, distinguishes only to be, the function of TMAl and TMGa flow is different from embodiment 1, is specially: the TMAl flow in gradual change AlGaN layer drops to 5 sccm from 100 sccm, and its function is C=100-95 x 3(sccm), the TMGa flow is raised to 15 sccm from 3 sccm linearities, and its function curve is G=12 x+ 3 (sccm).In above-mentioned two functions x(0≤ x≤ 1) for the normalization time of gradual change AlGaN layer growth.Function curve as shown in Figure 2.
For the preparation method's of a kind of gradual change AlGaN layer of the present invention validity better is described, take linear function of the prior art as a comparison especially, substantially similar in itself and embodiment, difference only is that the function of TMAl and TMGa flow is different from embodiment 1, adopt linear function, be specially: in gradual change AlGaN layer growth process, the TMAl flow drops to 5 sccm from 100 sccm linearities, and its function curve is D=100-95 x(sccm); The TMGa flow is raised to 15 sccm from 3 sccm linearities, and its function curve is G=12 x+ 3 (sccm).In above-mentioned two functions x(0≤ x≤ 1) for the normalization time of gradual change AlGaN layer growth.Function curve as shown in Figure 2.
Below with reference to a plurality of experimental results in Fig. 3-6, above three embodiment and prior art are compared explanation, with the preparation method's that proves absolutely a kind of gradual change AlGaN of the present invention layer validity.
As shown in Figure 3, be X-ray diffraction (XRD) intensity distribution of the gradual change AlGaN layer of three embodiment and prior art, as can be seen from Figure, its XRD intensity distributions is different.XRD intensity is generally determined by film thickness and crystal mass.Here, except the flow function difference of TMAl, other growth conditionss are identical, and therefore, XRD intensity is only determined by film thickness.
As shown in Figure 3, than prior art, the strength ratio of the low al composition AlGaN of embodiment 2 and embodiment 3 a little less than, the intensity of high aluminium component AlGaN is more intense, the Thickness Ratio of low al composition AlGaN that embodiment 2 and embodiment 3 are described is thinner, and high aluminium component AlGaN is thicker.
For embodiment 1, when we deliberately accelerate its gradual change AlGaN layer at the rate of change of large TMAl flow, and delay it when the rate of change of little TMAl flow, obviously seen the intensity enhancing in its low al composition zone in Fig. 3, and the remitted its fury in its high aluminium component zone.
The result of Fig. 3 has proved absolutely, adopts different TMAl flow functions, and in the gradual change AlGaN of same thickness layer, the distribution of its al composition is different.This TMAl flow that different functions also just have been described is significantly, effectively to the regulation and control that the al composition of gradual change AlGaN layer distributes.
As shown in Figure 4, we have also adopted secondary ion mass spectrometry (SIMS) to study with the al composition distribution of implementing 2 implementing 1, find that the al composition distribution of enforcement 1 and embodiment 2 differs widely really.
As shown in Figure 4, the al composition of embodiment 1 descends soon than the high aluminium component stage at gradual change AlGaN layer, descends slowly in the low al composition stage, is complementary with the TMAl changes in flow rate rule of the parabola (function A) of Fig. 2 opening upwards.
For embodiment 2, when adopting the TMAl flow of the parabola (function B) that Open Side Down, its al composition ratio is from high aluminium component (Al 0.55Ga 0.45N) in the change procedure of low al composition, be almost linear.This is because the TMAl flow of the parabola (function B) that Open Side Down has two effects: one, increased the TMAl total amount that passes into reative cell, compensated TMAl and NH 3The used up TMAl of pre-reaction; Two, delayed the rate of change of TMAl in the time of large flow (i.e. compared to existing technology linear function, AlGaN layer thickness when having increased large flow TMAl), accelerated the rate of change of TMAl the low discharge time (i.e. compared to existing technology linear functional relation, AlGaN layer thickness when having reduced low discharge TMAl), so just regulated the distribution of al composition in gradual change AlGaN layer, the Al component that has formed intimate linearity distributes.
Therefore, in Fig. 4, the SIMS test result of embodiment 1 and embodiment 2 has illustrated that also the regulation and control that the TMAl flow of different functions distributes to al composition in gradual change AlGaN layer are significantly, effectively.
As shown in Figure 5, Raman test result schematic diagram for the suffered biaxial stress of GaN film of three embodiment of the present invention and prior art, by can very significantly find out in figure, the suffered biaxial stress of the GaN film of three embodiment and prior art is different, from the tensile stress variations to the compression.This has illustrated that also the regulating and controlling effect of gradual change AlGaN layer counter stress is significantly, effectively.
Also can see from Fig. 5, adopt the method growth gradual change AlGaN layer of prior art, although compression has appearred in its GaN film, but the compression of embodiment 2 and embodiment 3 is greater than the compression of prior art, this explanation, growing method of the present invention more is conducive to grow the thicker GaN film that does not chap.Observed drawing by experiment, 1 μ m gradual change AlGaN layer of the function growth of the TMAl flow of the employing parabola (function B) that Open Side Down, its 3 μ m GaN films of growing above do not chap.And 1 μ m gradual change AlGaN layer of the function of the linear TMAl flow of prior art growth, its 3 μ m GaN films of growing above chap.
As shown in Figure 6, halfwidth comparison diagram for the XRD swing curve of three embodiment of the present invention and prior art, the halfwidth of the XRD swing curve of the GaN (002) of the halfwidth of the XRD swing curve of three embodiment and prior art is more similar, and the XRD swing curve halfwidth of the GaN of embodiment 2 (002) is minimum, this is maximum because of the suffered compression of the GaN film in embodiment 2, and compression can reduce edge dislocation and mixed dislocation.
In conjunction with Fig. 5 and Fig. 6, can find out, for three embodiment and prior art, when the tensile stress minimizing, when compression increased, the halfwidth of its GaN (102) reduced (being that edge dislocation and mixed dislocation reduce), and vice versa.
This shows, the gradual change AlGaN layer counter stress that the component distribution that the preparation method of a kind of gradual change AlGaN layer of the present invention obtains is different and the regulating and controlling effect of crystal mass are significantly, effectively.
Above-described embodiment is better embodiment of the present invention; it should be understood that; above-described embodiment is not limited to the present invention; those of ordinary skill in the art is not in the situation that break away from the aim of principle of the present invention; variation, modification, replacement and distortion that above-described embodiment is made are within all should falling into protection scope of the present invention.

Claims (10)

1. the preparation method of a gradual change AlGaN layer is before growth gradual change AlGaN layer, at first at Grown one deck AlN resilient coating; The method of growth gradual change AlGaN layer is: pass into NH in reative cell 3, trimethyl aluminium and trimethyl gallium, the trimethyl aluminium flow that wherein passes into reduces gradually, TMGa flow rate increases gradually; It is characterized in that,
The function of trimethyl aluminium flow is:
Figure 962292DEST_PATH_IMAGE001
The function of TMGa flow rate is:
Figure 4066DEST_PATH_IMAGE002
Wherein, x is the normalization time of gradual change AlGaN layer growth, and m, n are not 1 simultaneously.
2. the preparation method of gradual change AlGaN layer according to claim 1, is characterized in that, the growing method of described gradual change AlGaN layer is Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, chemical beam epitaxy method or hydride vapour phase epitaxy method.
3. the preparation method of gradual change AlGaN layer according to claim 2, is characterized in that, described gradual change AlGaN layer growth temperature is 900 ~ 1100 ℃, and growth pressure is 50 ~ 200 mbar, and the V/III ratio is 500 ~ 4000.
4. the preparation method of gradual change AlGaN layer according to claim 1, is characterized in that, described gradual change AlGaN layer thickness is 0.8 ~ 2 μ m.
5. the preparation method of gradual change AlGaN layer according to claim 1, is characterized in that, the range of flow of described trimethyl aluminium is 400 ~ 0sccm, and the range of flow of trimethyl gallium is 0 ~ 200 sccm.
6. the preparation method of gradual change AlGaN layer according to claim 5, is characterized in that, the range of flow of described trimethyl aluminium is 100 ~ 5sccm, and the range of flow of described trimethyl gallium is 3 ~ 15 sccm.
7. the preparation method of gradual change AlGaN layer according to claim 1, it is characterized in that, the growing method of described AlN resilient coating and GaN film is Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, chemical beam epitaxy method or hydride vapour phase epitaxy method.
8. the preparation method of gradual change AlGaN layer according to claim 1, is characterized in that, the thickness range of described AlN resilient coating is 50 ~ 300nm.
9. the preparation method of gradual change AlGaN layer according to claim 1, is characterized in that, described substrate is Si substrate, SiC substrate or Sapphire Substrate.
10. the device that the preparation method who adopts the described gradual change AlGaN of claim 1-9 layer obtains, is characterized in that, comprises successively from the bottom up substrate, AlN resilient coating and gradual change AlGaN layer.
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CN103311396A (en) * 2013-06-19 2013-09-18 南宁市柳川华邦电子有限公司 Diode with Si-based substrate
CN103474331A (en) * 2013-10-08 2013-12-25 中国电子科技集团公司第四十四研究所 Method for growing epitaxy AlN template on sapphire substrate
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CN106816363A (en) * 2017-01-12 2017-06-09 西安电子科技大学 Based on m faces Al2O3Semi-polarity AlN films of graph substrate and preparation method thereof
CN111534855A (en) * 2020-05-09 2020-08-14 新磊半导体科技(苏州)有限公司 Molecular beam epitaxial growth method of multi-component composition gradient layer

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