CN116978984B - Molecular beam epitaxial growth method of QWIP device - Google Patents

Molecular beam epitaxial growth method of QWIP device Download PDF

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CN116978984B
CN116978984B CN202311237686.1A CN202311237686A CN116978984B CN 116978984 B CN116978984 B CN 116978984B CN 202311237686 A CN202311237686 A CN 202311237686A CN 116978984 B CN116978984 B CN 116978984B
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gallium source
source furnace
molecular beam
polar
furnace
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CN116978984A (en
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郭帅
杜全钢
冯巍
谢小刚
李维刚
苏大鸿
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Xinlei Semiconductor Technology Suzhou Co ltd
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P

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Abstract

The invention provides a molecular beam epitaxial growth method of a QWIP device, and relates to the technical field of semiconductor manufacturing. The method comprises the following steps: according to Al x Ga 1‑x The component x in the As layer determines the beam rate of aluminum molecules and the beam rate of gallium molecules; selecting two gallium source furnaces; according to polar angle theta Al And polar angle theta Ga2 For V Ga1 Respectively calculating uniformity index values, and respectively calculating V corresponding to the minimum index value Ga1 As a selected value; stabilizing the beam flow rate of the first gallium source furnace to a selected value, and stabilizing the beam flow rate of the second gallium source furnace to V Ga The difference of the selected values is subtracted. And providing gallium molecular beams by adopting two gallium source furnaces, and selecting the optimal beam flow rate of the first gallium source furnace by calculating the uniformity index value, so as to obtain the beam flow rate of the second gallium source furnace. With this growth condition, the uniformity of the Al composition in the barrier layer can be improved, thereby improving the uniformity of the qwi device epitaxial wafer.

Description

Molecular beam epitaxial growth method of QWIP device
Technical Field
The invention relates to the technical field of semiconductor manufacturing, in particular to a molecular beam epitaxial growth method of a QWIP device.
Background
In recent years, photo-sensing technology presents a new situation that is actively developed, and these developments all depend on the progress of optoelectronic technology. Various optoelectronic devices will play a key role in future optical sensing systems, wherein the detector used for optical detection is the core device of the optical sensing system.
The quantum well infrared detector (QWIP, quantum Well Infrared Photodetector) technology is a high and new technology developed in the 90 th century, and compared with other infrared technologies, the QWIP has the advantages of high response speed, good uniformity, easiness in manufacturing a bicolor and polychromatic large area array and the like, so that the QWIP becomes a hot spot for infrared focal plane research.
For QWIP devices of GaAs/AlGaAs material system, the Al component of AlGaAs barrier layer in GaAs/AlGaAs superlattice seriously affects the detection wavelength of the device and the performance parameters of dark current and the like, so in order to obtain a detector array with excellent performance, the epitaxial growth process needs to be optimized to obtain an epitaxial wafer with large-area and uniform Al component of AlGaAs barrier layer. In the process of growing qwi p devices using molecular beam epitaxy, for example, the uniformity of qwi p device epitaxial wafers can be improved by optimizing the rotation speed of the sample holder of the molecular beam epitaxy apparatus, however, such improvement is relatively limited, and in order to further improve the uniformity of qwi p device epitaxial wafers, a new molecular beam epitaxy method needs to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a molecular beam epitaxial growth method of a QWIP device, so as to solve the problem of improving the uniformity of an epitaxial wafer of the QWIP device.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a molecular beam epitaxial growth method of a QWIP device, which comprises a multi-quantum well structure, wherein a barrier layer in the multi-quantum well structure is Al x Ga 1-x An As layer, wherein x represents an Al component, and 0<x<The well layer in the multi-quantum well structure is a GaAs layer, the molecular beam epitaxy device for epitaxially growing the QWIP device comprises an aluminum source furnace and a plurality of gallium source furnaces, and the aluminum source furnace and the gallium source furnaces are arranged on the circumference of the bottom of a growth chamber of the molecular beam epitaxy device, and the method comprises the following steps:
according to Al x Ga 1-x The composition x in the As layer, predetermined epitaxially grown Al x Ga 1-x Average of aluminum molecular beam required for As layerBeam Rate V Al Average beam flow velocity V of gallium molecular beam Ga The average beam velocity represents the beam velocity of the molecular beam at the center point position of the substrate support plate carried by the molecular beam epitaxy apparatus;
selecting two gallium source furnaces from the plurality of gallium source furnaces to collectively provide an average beam current rate of V Ga Two gallium source furnaces including a first gallium source furnace and a second gallium source furnace, and V Ga =V Ga1 +V Ga2 Wherein V is Ga1 Representing the average beam current rate of the first gallium source furnace, V Ga2 Represents the average beam current rate of the second gallium source furnace, 0<V Ga1 <V Ga And the positional relationship of the first gallium source furnace, the second gallium source furnace and the aluminum source furnace is as follows: a polar coordinate system is established in a plane where the substrate supporting plate is positioned by taking the central point of the substrate supporting plate carried by the molecular beam epitaxy equipment as a pole, a ray formed by connecting the pole and a vertical projection point of the center of a furnace mouth of a first gallium source furnace on the plane is taken as a polar axis, and the polar angle of the vertical projection point of the center of the furnace mouth of a second gallium source furnace on the plane is theta Ga2 The polar angle of the vertical projection point of the center of the furnace mouth of the aluminum source furnace on the plane is theta Al ；
According to polar angle theta Al And polar angle theta Ga2 For V Ga1 Each of a plurality of different values of (1) respectively calculating a corresponding uniformity index value, and corresponding V to the smallest uniformity index value Ga1 As a selected value of the average beam rate of the first gallium source furnace, the uniformity index value is obtained by calculating as follows: calculating the ratio of the deposition thickness of the aluminum molecular beam to the deposition thickness of the gallium molecular beam at a plurality of different positions on the substrate supporting plate in a preset time period to obtain a plurality of ratios, and then calculating the relative standard deviation of an array formed by the plurality of ratios, wherein the relative standard deviation is used as a uniformity index value;
stabilizing the average beam flow rate of the first gallium source furnace to a selected value, and stabilizing the average beam flow rate of the second gallium source furnace to V Ga Subtracting the selected value to obtain a difference value, and stabilizing the average beam flow rate of the aluminum source furnace to be V Al The first gallium source furnace and the second gallium source furnace are then utilized to provide Al in the grown multi-quantum well structure x Ga 1-x Gallium molecular beam required for As layer and GaAs layer, al in growing multiple quantum well structure is provided by using aluminum source furnace x Ga 1-x The As layer requires a beam of aluminum molecules.
Optionally, in calculating the relative standard deviation, a plurality of different locations on the substrate pallet are selected as follows:
selecting one or more polar paths in a polar coordinate system, selecting a plurality of polar angles at equal intervals in the range of 0 to 2 pi for each of the one or more polar paths, taking the corresponding positions of coordinates formed by the selected polar paths and the polar angles on a substrate supporting plate as the plurality of different positions, wherein any one of the one or more polar paths ρ satisfies the following range: 0<ρ<r 0 Wherein r is 0 Representing the radius of the substrate carrier.
Optionally, for each of the one or more polar paths, the polar angle has a value of: 0. pi/6, pi/3, pi/2, 2 pi/3, 5 pi/6, pi, 7 pi/6, 4 pi/3, 3 pi/2, 5 pi/3, 11 pi/6.
Optionally, the number of pole diameters selected is 1, and the pole diameter is equal to r 0 /2。
Alternatively V Ga1 The selection modes of the plurality of different values are as follows: at 0 to V Ga Within a range of 0.05 ∙ V Ga Will be from 0.05 ∙ V for step size Ga To 0.95 and ∙ V Ga Is taken as the V Ga1 Is a plurality of different values.
Alternatively, the thickness H of the barrier layer in the multiple quantum well structure B In the range of 40nm<H B <Thickness H of well layer in 60nm multiple quantum well structure W In the range of 4nm<H W <6nm。
Optionally, the number of periods n of the barrier layer/well layer in the multiple quantum well structure is in the range of 20< n <60.
Alternatively, al x Ga 1-x The component x in the As layer ranges from 0.2<x<0.5, average beam velocity V Al The range of (2) is: 0.1 Mu m/h<V Al <0.5 μm/h。
The beneficial effects of the invention include:
the molecular beam epitaxial growth method of the QWIP device provided by the invention comprises the following steps: according to Al x Ga 1-x The composition x in the As layer, predetermined epitaxially grown Al x Ga 1-x Average beam flow velocity V of aluminum molecular beam required for As layer Al Average beam flow velocity V of gallium molecular beam Ga The average beam velocity represents the beam velocity of the molecular beam at the center point position of the substrate support plate carried by the molecular beam epitaxy apparatus; selecting two gallium source furnaces from the plurality of gallium source furnaces to collectively provide an average beam current rate of V Ga Two gallium source furnaces including a first gallium source furnace and a second gallium source furnace, and V Ga =V Ga1 +V Ga2 Wherein V is Ga1 Representing the average beam current rate of the first gallium source furnace, V Ga2 Represents the average beam current rate of the second gallium source furnace, 0<V Ga1 <V Ga And the positional relationship of the first gallium source furnace, the second gallium source furnace and the aluminum source furnace is as follows: a polar coordinate system is established in a plane where the substrate supporting plate is positioned by taking the central point of the substrate supporting plate carried by the molecular beam epitaxy equipment as a pole, a ray formed by connecting the pole and a vertical projection point of the center of a furnace mouth of a first gallium source furnace on the plane is taken as a polar axis, and the polar angle of the vertical projection point of the center of the furnace mouth of a second gallium source furnace on the plane is theta Ga2 The polar angle of the vertical projection point of the center of the furnace mouth of the aluminum source furnace on the plane is theta Al The method comprises the steps of carrying out a first treatment on the surface of the According to polar angle theta Al And polar angle theta Ga2 For V Ga1 Each of a plurality of different values of (1) respectively calculating a corresponding uniformity index value, and corresponding V to the smallest uniformity index value Ga1 As a selected value of the average beam rate of the first gallium source furnace, the uniformity index value is obtained by calculating as follows: calculating the ratio of the deposition thickness of the aluminum molecular beam to the deposition thickness of the gallium molecular beam at a plurality of different positions on the substrate supporting plate in a preset time period to obtain a plurality of ratios, and then calculating the phase of an array formed by the plurality of ratiosRegarding the standard deviation, regarding the relative standard deviation as a uniformity index value; stabilizing the average beam flow rate of the first gallium source furnace to a selected value, and stabilizing the average beam flow rate of the second gallium source furnace to V Ga Subtracting the selected value to obtain a difference value, and stabilizing the average beam flow rate of the aluminum source furnace to be V Al The first gallium source furnace and the second gallium source furnace are then utilized to provide Al in the grown multi-quantum well structure x Ga 1-x Gallium molecular beam required for As layer and GaAs layer, al in growing multiple quantum well structure is provided by using aluminum source furnace x Ga 1-x The As layer requires a beam of aluminum molecules. And providing gallium molecular beams by adopting two gallium source furnaces, and selecting the optimal beam flow rate of the first gallium source furnace by calculating the uniformity index value, so as to obtain the beam flow rate of the second gallium source furnace. With this growth condition, the uniformity of the Al composition in the barrier layer can be improved, thereby improving the uniformity of the qwi device epitaxial wafer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a molecular beam epitaxy growth method of a qwi device according to an embodiment of the present invention;
fig. 2 shows a schematic structural diagram of a qwi device according to an embodiment of the present invention;
FIG. 3 is a schematic plan view of a growth chamber of a molecular beam epitaxy apparatus according to an embodiment of the present invention;
fig. 4 shows a graph of normalized relative standard deviation versus average beam current rate for a first gallium source furnace provided by an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
For QWIP devices of GaAs/AlGaAs material system, the Al component of AlGaAs barrier layer in GaAs/AlGaAs superlattice seriously affects the detection wavelength of the device and the performance parameters of dark current and the like, so in order to obtain a detector array with excellent performance, the epitaxial growth process needs to be optimized to obtain an epitaxial wafer with large-area and uniform Al component of AlGaAs barrier layer. In the process of growing qwi p devices using molecular beam epitaxy, for example, the uniformity of qwi p device epitaxial wafers can be improved by optimizing the rotation speed of the sample holder of the molecular beam epitaxy apparatus, however, such improvement is relatively limited, and in order to further improve the uniformity of qwi p device epitaxial wafers, a new molecular beam epitaxy method needs to be developed.
Fig. 1 is a schematic flow chart of a molecular beam epitaxy growth method of a qwi device according to an embodiment of the present invention; fig. 2 shows a schematic structural diagram of a qwi device according to an embodiment of the present invention; fig. 3 is a schematic plan view of a growth chamber of a molecular beam epitaxy apparatus according to an embodiment of the present invention. The present invention will be described in detail below with reference to fig. 1 to 3.
As shown in fig. 2, the structure of the qwi device is sequentially, from bottom to top, a substrate 201, a buffer layer 202, a lower ohmic contact layer 203, a multiple quantum well structure 204, an upper barrier layer 205 and An upper ohmic contact layer 206, wherein the multiple quantum well structure 204 is formed by repeatedly and periodically stacking barrier layers, for example, the multiple quantum well structure 204 is formed by stacking a barrier layer A1/well layer B1, a barrier layer A2/well layer B2, …, and a barrier layer An/well layer Bn, n represents the number of periods, and optionally, the number of periods n of the barrier layer/well layer in the multiple quantum well structure 204 ranges from 20< n <60, for example, n may take values of 30, 40 or 50, etc. according to the structural design. The barrier layer A1, the barrier layers A2, …, and the barrier layer An are the same material as each other and have the same thickness; also, the well layer B1, the well layers B2, …, and the well layer Bn are the same material as each other and have the same thickness. It should be appreciated that the method provided by the embodiments of the present invention only relates to the multiple quantum well structure 204 in the qwi device structure, and thus the qwi device structure in the embodiments of the present invention may not be limited to the above-described structure, for example, the structure of the qwi device may also include other epitaxial layer structures besides the multiple quantum well structure 204, as long as the multiple quantum well structure 204 is included in the structure of the qwi device.
In An embodiment of the present invention, the barrier layers (including barrier layer A1, barrier layers A2, …, barrier layer An shown in FIG. 2) in the multiple quantum well structure 204 are Al x Ga 1-x An As layer, wherein x represents an Al component, and 0<x<1, optionally Al x Ga 1-x The component x in the As layer ranges from 0.2<x<0.5. Alternatively, the thickness H of the barrier layers (i.e., each of barrier layer A1, barrier layers A2, …, barrier layer An) in the multiple quantum well structure B In the range of 40nm<H B <60nm. The well layers (including the well layer B1, the well layers B2, …, and the well layer Bn shown in fig. 2) in the multiple quantum well structure 204 are GaAs layers. Alternatively, the thickness H of the well layer (i.e., each of the well layer B1, the well layer B2, …, the well layer Bn) in the multiple quantum well structure W In the range of 4nm<H W <6nm. Composition x, thickness H B Thickness H W The value of (2) is predetermined according to the function requirement of the device in the structural design stage.
In an embodiment of the present invention, a molecular beam epitaxy apparatus for epitaxially growing qwi p devices includes an aluminum source furnace and a plurality of gallium source furnaces, each of which is disposed on a circumference of a bottom of a growth chamber of the molecular beam epitaxy apparatus.
Fig. 3 shows a schematic plan view of a growth chamber of a molecular beam epitaxy apparatus according to an embodiment of the present invention, in fig. 3, a substrate carrier 302 is carried by a sample holder in a chamber 301, and an aluminum source furnace 306, a first gallium source furnace 304 and a second gallium source furnace 305 are all located at a bottom circumference of the chamber 301. It should be appreciated that other multiple source furnaces may also be included at the bottom circumference of the chamber 301. Typically, mass-production molecular beam epitaxy apparatus for epitaxial growth of group III-V elements include an aluminum source furnace, a plurality of gallium source furnaces, and other related source furnaces (e.g., silicon source furnace, arsenic source furnace, phosphorus source furnace, etc.), all of which are fixedly disposed on the circumference of the bottom of the growth chamber of the molecular beam epitaxy apparatus. In practice, once the molecular beam epitaxy apparatus for performing epitaxial growth is selected, the relative positional relationship between these source furnaces can be measured and determined.
As shown in fig. 3, for example, the substrate carrier 302 may simultaneously carry four substrates including a first substrate 331, a second substrate 332, a third substrate 333, and a fourth substrate 334, it being understood that the substrate carrier 302 may also be a substrate carrier carrying other numbers and/or sizes of substrates.
The molecular beam epitaxial growth method of the QWIP device provided by the embodiment of the invention comprises the following steps:
step 101, according to Al x Ga 1-x The composition x in the As layer, predetermined epitaxially grown Al x Ga 1-x Average beam flow velocity V of aluminum molecular beam required for As layer Al Average beam flow velocity V of gallium molecular beam Ga 。
The average beam velocity represents the beam velocity of the molecular beam at the center point position of the substrate carrier carried by the molecular beam epitaxy apparatus, i.e., the beam velocity of the molecular beam at the center point Q position of the substrate carrier 302 shown in fig. 3. As described below, for any source furnace, the beam velocity at different locations on the substrate support is non-uniform, and the average beam velocity is typically characterized by the beam velocity of the molecular beam at the center point location of the substrate support. The average beam current rate of the source furnace may be controlled and regulated by the heating power or temperature of the source furnace.
In practical application, al x Ga 1-x The component x in the As layer is a preset fixed value, and the value of x is determined by structural design. By selecting an appropriate average beam flow velocity V of the aluminum molecular beam Al Average beam flow velocity V of gallium molecular beam Ga Can realize growth to obtain Al x Ga 1-x And an As layer. For a determined value of x, the average beam velocity V Al And average beam velocity V Ga Is determined.Therefore, the average beam velocity V can be selectively determined according to the use condition of the molecular beam epitaxy equipment Al And average beam velocity V Ga After one of them, the average beam velocity V is determined according to the value of x Al And average beam velocity V Ga Another of which is described in detail below. For example, when x=0.3 is determined in the structural design, if V is selected Al The value of (2) is 0.3 mu m/h, V can be calculated and obtained Ga The value of (2) was 0.7 μm/h. Similarly, when x=0.25 is determined in the structural design, if V is selected Ga The value of (2) is 0.9 mu m/h, V can be calculated and obtained Al The value of (2) is 0.3 μm/h. Alternatively, the average beam flow rate V Al The range of (2) is: 0.1 Mu m/h<V Al <0.5 Mu.m/h, in which case V may be preselected according to a range within this range Al The value of (2) and the value of the component x are calculated to obtain the corresponding V Ga Is a value of (2).
Step 102, selecting two gallium source furnaces from the gallium source furnaces to jointly provide an average beam current rate of V Ga Gallium molecular beams of (a).
In molecular beam epitaxy, multiple gallium source furnaces may be employed to collectively provide a gallium molecular beam. For example, in the present invention, two gallium source furnaces may be employed to collectively provide an average beam current rate of V Ga Gallium molecular beams of (a). The two gallium source furnaces in the present invention include a first gallium source furnace 304 and a second gallium source furnace 305. Wherein V is Ga =V Ga1 +V Ga2 Wherein V is Ga1 Represents the average beam current rate, V, of the first gallium source furnace 304 Ga2 Represents the average beam rate of the second gallium source furnace 305, where 0<V Ga1 <V Ga . Due to V Ga Has been determined in step 101, so only V is determined Ga1 And V Ga2 One of which is determined.
It should be appreciated that the molecular beam epitaxy apparatus may include two or more gallium source furnaces, in the present invention, two of the gallium source furnaces are selected from the plurality of gallium source furnaces to collectively provide an average beam rate of V Ga Gallium molecular beams of (a).
In the present invention, as shown in fig. 3, a first gallium source furnace 304, a second gallium source furnace 305, and an aluminum source furnace 306 are as follows: taking the central point Q of a substrate supporting plate 302 carried by molecular beam epitaxy equipment as a pole, establishing a polar coordinate system in a plane of the substrate supporting plate 302, taking a ray formed by connecting the pole Q with a vertical projection point P of the center of a furnace mouth of a first gallium source furnace 304 on the plane as a polar axis, wherein the polar angle of a vertical projection point N of the center of a furnace mouth of a second gallium source furnace 305 on the plane is theta Ga2 (i.e. < NQP), the polar angle of the perpendicular projection point M of the center of the furnace mouth of the aluminum source furnace 306 on the plane is θ Al (i.e. < MQP).
Alternatively, to select a source furnace position that is more advantageous for improving the uniformity of Al composition, the polar angle θ Ga2 (i.e. < NQP) is greater than 0 and less than pi, polar angle θ Al (i.e. < MQP) is greater than 0 and less than the polar angle θ Ga2 (that is, the angle MQP is less than the angle NQP), in other words, the above positional relationship indicates that the aluminum source furnace is on the minor arc (not on the major arc) defined by the two gallium source furnaces on the circumference of the bottom of the growth chamber. In general, for a mass production type molecular beam epitaxy apparatus including one aluminum source furnace and a plurality of gallium source furnaces, the positional relationship of the first gallium source furnace 304, the second gallium source furnace 305, and the aluminum source furnace 306 described above is easily satisfied by selecting an appropriate gallium source furnace as the first gallium source furnace 304.
It will be appreciated that for the selected device, the polar angle θ described above Al And polar angle theta Ga2 The value of (2) may be obtained by a preliminary measurement.
Step 103, according to the polar angle theta Al And polar angle theta Ga2 For V Ga1 Each of a plurality of different values of (1) respectively calculating a corresponding uniformity index value, and corresponding V to the smallest uniformity index value Ga1 As a selected value for the average beam rate of the first gallium source furnace.
The uniformity index value is obtained by the following calculation: ratios of the aluminum molecular beam deposition thickness to the gallium molecular beam deposition thickness at a plurality of different positions on the substrate support plate 302 over a preset period of time are calculated, thereby obtaining a plurality of ratios, and then a relative standard deviation of an array consisting of the plurality of ratios is calculated as a uniformity index value.
For any source furnace, the beam rate is non-uniform at different locations on the substrate support plate 302, and the beam rate is greater at locations on the substrate support plate 302 closer to the source furnace when the substrate support plate 302 is stationary, and thus, the uniformity of the deposition thickness at different locations on the substrate support plate 302 can be improved by rotating the substrate support plate 302, however, such improvement is relatively limited. Taking a gallium (Ga) source furnace as an example, ga beam deposition rates at different positions on a substrate supporting plate satisfy the following relation: 。
wherein the method comprises the steps ofVr(r, θ, t) represents the Ga flux deposition rate at different times at different positions on the substrate support plate, α is a coefficient obtained based on the whole substrate support plate growth rate data fitting, α is a fixed value and α can be obtained by a pre-test for a fixed molecular beam epitaxy apparatus, and for different source furnaces of the same apparatus, the values of α can be considered equal, r represents the distance from the center of the substrate support plate, θ represents the azimuth angle (i.e., the polar angle in the polar coordinate system described above), θ 1 Representing the phase shift based on the Ga source furnace position (i.e., the polar angle of the Ga source furnace in the polar coordinate system described above), θ in the case of Ga source furnace position determination 1 Is a fixed value that can be obtained in advance. R is R 0 Indicating the rotational speed of the substrate support (i.e., the rotational speed of the sample holder) in revolutions per minute; t represents time in minutes; vr (Vr) 0 The deposition rate at the center point position of the substrate carrier, i.e., the average beam rate, is indicated. Integrating the time t for the above relationship can obtain the deposition thickness profile at different locations on the substrate support plate over a predetermined period of time. For example, for slave time t 1 To time t 2 The time period between the two times is integrated by the relation, and the time t is obtained 1 To time t 2 Deposition thickness of Ga source furnace at different positions on substrate palletVr(r, θ) is:。
for the first gallium source furnace 304 shown in fig. 3, θ in the polar coordinate system established in the above 1 =0, so that it is possible to obtain:，
Vr Ga 1 (r, θ) represents the Ga molecular beam deposition thickness provided by the first gallium source furnace 304 at different locations on the substrate support (from time t 1 To time t 2 Time period in between).
For the second gallium source furnace 305 shown in fig. 3, θ in the polar coordinate system established hereinabove 1 =θ Ga2 Thus, it is possible to obtain:，
Vr Ga 2 (r, θ) represents the Ga molecular beam deposition thickness provided by the second gallium source furnace 305 at different locations on the substrate support (from time t 1 To time t 2 Time period in between).
It should be understood that in the case where the gallium molecular beams are supplied from the first gallium source furnace 304 and the second gallium source furnace 305 together, the total thickness of the Ga molecular beam deposition supplied at different positions on the substrate support plate is the total thickness of the Ga molecular beam deposition supplied from the first gallium source furnace 304 and the second gallium source furnace 305, that is:。
Vr Ga (r, θ) represents the total thickness of Ga molecular beam deposition provided by the first gallium source furnace 304 and the second gallium source furnace 305 at different locations on the substrate support (from time t 1 To time t 2 Time period in between).
For the aluminum source furnace 306 shown in FIG. 3, θ in the polar coordinate system established hereinabove 1 =θ Al It is possible to obtain: 。
Vr Al (r, θ) represents the Al molecular beam deposition thickness provided by the aluminum source furnace 306 at different locations on the substrate support (from time t 1 To time t 2 Time period in between).
In order to further improve the uniformity of the Al component of the AlGaAs barrier layer at different locations on the substrate support plate, i.e., at different locations on the substrate support plate within a predetermined period of time (corresponding to the growth time of the AlGaAs barrier layer)Vr Al (r, θ) andVr Ga uniformity of ratio of (r, θ).
From the aboveVr Ga1 (r,θ)、Vr Ga2 (r, θ) andVr Al the expression of (r, θ) shows that for a fixed value of r, the value of r is within a fixed time range (i.e., t 1 And t 2 Fixed value of (c) of the code pattern,Vr Ga1 (r,θ)、Vr Ga2 (r, θ) andVr Al (r, θ) are composed of two parts, a constant term and a trigonometric function term with respect to θ. For simplicity of calculation, the above is followedVr Ga1 (r,θ)、Vr Ga2 (r, θ) andVr Al the expression of (r, θ) is simplified.
Represented by S1Vr Ga1 Trigonometric function term of (r, θ), denoted by S2Vr Ga2 Trigonometric function term of (r, θ), denoted by S3Vr Al The trigonometric function term of (r, θ) is as follows:；；。
order theAnd applying a trigonometric function and a difference product formula to the above three formulas, which can be modified as: />；；/>。
At this time, at different positions on the substrate carrierVr Al (r, θ) andVr Ga the ratio Tr (r, θ) of (r, θ) can be expressed as:。
for any fixed R value, due to R 0 Is preselected and fixed, within a fixed time frame (i.e., t 1 And t 2 Fixed value of (a), the value of beta is fixed, tr (r, theta) can be regarded as a function of theta, and at this time, for a plurality of values of theta in the range of 0 to 2 pi, a plurality of Tr values are correspondingly obtained, and the relative standard deviation St of the plurality of Tr values can be calculated and obtained Tr And relative standard deviation St Tr As a uniformity index value. Obviously, the relative standard deviation St Tr The smaller the value of (c) is, the better the uniformity of Tr value with changes in θ is.
Optionally, in calculating the relative standard deviation, a plurality of different locations on the substrate pallet are selected as follows: in a polar coordinate system, selecting one or more polar paths, for each of the one or more polar paths, selecting a plurality of polar angles θ at equal intervals in a range of 0 to 2Ω, taking a corresponding position of coordinates made up of the selected polar path and polar angle on the substrate pallet as the plurality of different positions, any one of the one or more polar paths ρ (i.e., r in the above formula) satisfying the following range: 0<ρ<r 0 Wherein r is 0 Representing the radius of the substrate carrier. Optionally, for the subjectEach of the one or more polar paths has a value of a polar angle θ:0. pi/6, pi/3, pi/2, 2 pi/3, 5 pi/6, pi, 7 pi/6, 4 pi/3, 3 pi/2, 5 pi/3, 11 pi/6. In summary, when selecting a plurality of different locations on the substrate carrier, the circumferential location is selected by the polar diameter, and then the location of the point on the circumference is defined by the polar angle.
For example, in the case where the polar angle θ is 0, pi/6, pi/3, pi/2, 2pi/3, 5pi/6, pi, 7pi/6, 4pi/3, 3pi/2, 5pi/3, 11pi/6 at equal intervals for any one of the polar diameters ρ, the number of values of θ at this time is 12, 12 Tr values can be calculated correspondingly for the polar diameter ρ and the above 12 θ values, and then the relative standard deviation St of these 12 Tr values can be calculated Tr 。
A plurality of values of θ fixed in a range of 0 to 2ρ, for example, for a certain polar diameter ρ 0 And in the case where the value of θ is fixed to the aforementioned 12 values in the range of 0 to 2π, at this time, V Al And V Ga In the case of determination, if V Ga1 The values are different, and the relative standard deviation St obtained by corresponding calculation is corresponding Tr The values of (2) may also be different, as shown in FIG. 4, in other words, although V Ga =V Ga1 +V Ga2 But since the first gallium source furnace and the second gallium source furnace are positioned differently, when V Ga1 At V Ga When the ratio of the Al component to the AlGaAs barrier layer is different, the uniformity of the Al component of the AlGaAs barrier layer is affected.
For a value at 0<V Ga1 <V Ga V within the range Ga1 Respectively calculating corresponding relative standard deviation St Tr Then determining the smallest relative standard deviation St Tr Corresponding V Ga1 Value of V Ga1 The value is taken as a selected value of the average beam rate of the first gallium source furnace 304. Alternatively V Ga1 The selection modes of the plurality of different values are as follows: at 0 to V Ga Within a range of 0.05 ∙ V Ga Will be from 0.05 ∙ V for step size Ga To 0.95 and ∙ V Ga Is taken as the V Ga1 Is a plurality of different values.
Specifically, for example, for a selected molecular beam epitaxy apparatus, the polar angle θ is measured Al Pi/3 and polar angle θ Ga2 When x=0.3 is determined in the structural design, if selection is made =3pi/4V Al The value of (2) is 0.3 mu m/h, V can be calculated and obtained Ga Is 0.7 μm/h and then is aimed at a value of 0<V Ga1 <V in the range of 0.7 μm/h Ga1 Calculating a corresponding relative standard deviation St Tr . Fig. 4 shows a graph of normalized relative standard deviation versus average beam current rate for a first gallium source furnace provided by an embodiment of the invention. For different values of the polar diameter rho, the polar angle theta is 12 values as follows: 0. pi/6, pi/3, pi/2, 2 pi/3, 5 pi/6, pi, 7 pi/6, 4 pi/3, 3 pi/2, 5 pi/3, 11 pi/6. In actual numerical calculations, e.g. V Ga1 The values of (2) may include 19 values from 0.035 μm/h to 0.665 μm/h in steps of 0.035 μm/h. In FIG. 4, curve 1 shows that the pole diameter ρ is equal to the set value r 0 Normalized relative standard deviation of the ratios Tr at the corresponding 12 positions at/6 is a function of the average beam flow rate V of the first gallium source furnace 304 Ga1 A relationship curve of the value change of (a); curve 2 shows that the polar diameter ρ is equal to the set value r 0 Normalized relative standard deviation of the ratios Tr at the corresponding 12 positions at/3 is a function of the average beam flow rate V of the first gallium source furnace 304 Ga1 A relationship curve of the value change of (a); curve 3 shows that the polar diameter ρ is equal to the set value r 0 Normalized relative standard deviation of the ratios Tr at the corresponding 12 positions at/2 is a function of the average beam flow rate V of the first gallium source furnace 304 Ga1 A relationship curve of the value change of (a); curve 4 shows that the polar diameter ρ is equal to the set value r 0 /6、r 0 /3、r 0 Normalized relative standard deviation of the ratio Tr at the corresponding 36 positions at/2 is a function of the average beam flow rate V of the first gallium source furnace 304 Ga1 A relationship curve of the value change of (a). As can be seen from curves 1 to 4, for the polar angle θ described above Al And polar angle theta Ga2 Taking into account only the relative standard deviation of the ratio Tr at the position corresponding to the polar diameter ρ equal to a certain set value or the positions corresponding to the polar diameters ρ equal to a plurality of set valuesThe relative standard deviation of the ratio Tr at the position, and the minimum value of the normalized relative standard deviation corresponds to the same V Ga1 The value corresponding to the minimum value of the normalized relative standard deviation in FIG. 4 Ga1 The value is 0.5 μm/h, at which time 0.5 μm/h may be the selected value for the average beam rate of the first gallium source furnace 304. As can be seen from FIG. 4, the minimum relative standard deviation corresponding V is calculated Ga1 In the course of the values, in order to reduce the amount of calculation, the position on the substrate carrier determined by only one polar diameter and its corresponding plurality of polar angles may be selected. For example, alternatively, in calculating the relative standard deviation, when selecting a plurality of different locations on the substrate carrier, the number of polar diameters selected is 1 and the polar diameter is equal to r 0 /2。
As can be seen from the above discussion, for different values of the average beam rate of the first gallium source furnace 304, when the average beam rate of the first gallium source furnace 304 is the selected value, the value of the relative standard deviation is the smallest, and at this time, at different positions on the substrate carrierVr Al (r, θ) andVr Ga the uniformity of the ratio Tr (r, θ) of (r, θ) is optimal.
Step 104, stabilizing the average beam flow rate of the first gallium source furnace to a selected value, and stabilizing the average beam flow rate of the second gallium source furnace to V Ga Subtracting the selected value to obtain a difference value, and stabilizing the average beam flow rate of the aluminum source furnace to be V Al The first gallium source furnace and the second gallium source furnace are then utilized to provide Al in the grown multi-quantum well structure x Ga 1-x Gallium molecular beam required for As layer and GaAs layer, al in growing multiple quantum well structure is provided by using aluminum source furnace x Ga 1-x The As layer requires a beam of aluminum molecules.
After determining the average beam current velocity V of the first gallium source furnace 304 according to step 103 Ga1 When stabilized to a selected value, can be based on V Ga2 =V Ga -V Ga1 An average beam current rate value for the second gallium source furnace 305 is determined. From the above analysis, it can be seen that the growth conditions can be used to improve the growth of the substrate at different locations on the substrate supportVr Al (r, θ) andVr Ga average of ratio Tr (r, θ) of (r, θ)Uniformity, and thus the uniformity of the Al composition of the AlGaAs barrier layer, improves the uniformity of the qwi device epitaxial wafer.
In practice, for example, when x=0.3 is determined in the structural design, if the selection is madeV Al The value of (2) is 0.3 mu m/h, V can be calculated and obtained Ga Is 0.7 μm/h and then for V in the range of 0 to 0.7 μm/h Ga1 Respectively calculating a corresponding uniformity index value (relative standard deviation St Tr ) If at V Ga1 In the case of =0.5 μm/h, the uniformity index value is the smallest, then V will be Ga1 =0.5 μm/h as the selected value, V at this time Ga2 = V Ga -V Ga1 =0.2 μm/h; then the average beam current rate of the first gallium source furnace 304 was stabilized to 0.5 μm/h, the average beam current rate of the second gallium source furnace 305 was stabilized to 0.2 μm/h, the average beam current rate of the aluminum source furnace was stabilized to 0.3 μm/h, and then the first gallium source furnace 304 and the second gallium source furnace 305 were used to provide Al in the grown multi-quantum well structure x Ga 1-x Gallium molecular beam required for As layer and GaAs layer, al in growing multiple quantum well structure is provided by using aluminum source furnace x Ga 1-x The As layer requires a beam of aluminum molecules. At this time, al having good uniformity of the composition can be obtained x Ga 1-x And an As layer.
In summary, the present invention provides gallium molecular beams by using two gallium source furnaces, and selects the optimal beam current rate of the first gallium source furnace by calculating the uniformity index value, thereby obtaining the beam current rate of the second gallium source furnace. With this growth condition, the uniformity of the Al composition in the barrier layer can be improved, thereby improving the uniformity of the qwi device epitaxial wafer.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (8)

1. QWIP deviceThe molecular beam epitaxial growth method is characterized in that the QWIP device structure comprises a multi-quantum well structure, and a barrier layer in the multi-quantum well structure is Al x Ga 1-x An As layer, wherein x represents an Al component, and 0<x<1, a well layer in the multiple quantum well structure is a GaAs layer, a molecular beam epitaxy apparatus for epitaxially growing the qwi device includes an aluminum source furnace and a plurality of gallium source furnaces, both of which are disposed on a circumference of a bottom of a growth chamber of the molecular beam epitaxy apparatus, the method includes:
according to the Al x Ga 1-x The composition x in the As layer is predetermined to epitaxially grow the Al x Ga 1-x Average beam flow velocity V of aluminum molecular beam required for As layer Al Average beam flow velocity V of gallium molecular beam Ga The average beam velocity represents the beam velocity of the molecular beam at the center point of the substrate support plate carried by the molecular beam epitaxy apparatus;
selecting two gallium source furnaces from the plurality of gallium source furnaces to collectively provide an average beam current rate of V Ga The two gallium source furnaces include a first gallium source furnace and a second gallium source furnace, and V Ga =V Ga1 +V Ga2 Wherein V is Ga1 Representing the average beam velocity, V, of the first gallium source furnace Ga2 Representing the average beam rate of the second gallium source furnace, wherein 0<V Ga1 <V Ga And the positional relationship of the first gallium source furnace, the second gallium source furnace, and the aluminum source furnace is as follows: a polar coordinate system is established in a plane where the substrate supporting plate is located by taking the central point of the substrate supporting plate borne by the molecular beam epitaxy equipment as a pole, a ray formed by connecting the pole and a vertical projection point of the center of a furnace mouth of the first gallium source furnace on the plane is taken as a polar axis, and the polar angle of the vertical projection point of the center of the furnace mouth of the second gallium source furnace on the plane is theta Ga2 The polar angle of the vertical projection point of the center of the furnace mouth of the aluminum source furnace on the plane is theta Al ；
According to polar angle theta Al And polar angle theta Ga2 For V Ga1 Each of a plurality of different values of (1) respectively calculating a corresponding uniformity index value, and corresponding V to the smallest uniformity index value Ga1 As a selected value of the average beam current rate of the first gallium source furnace, the uniformity index value is obtained by calculating: calculating the ratio of the deposition thickness of the aluminum molecular beam to the deposition thickness of the gallium molecular beam at a plurality of different positions on the substrate supporting plate within a preset time period to obtain a plurality of ratios, and then calculating the relative standard deviation of an array formed by the plurality of ratios, wherein the relative standard deviation is used as a uniformity index value;
stabilizing the average beam flow rate of the first gallium source furnace to the selected value, and stabilizing the average beam flow rate of the second gallium source furnace to V Ga Subtracting the difference value obtained by the selected value to stabilize the average beam flow rate of the aluminum source furnace to V Al And then using the first gallium source furnace and the second gallium source furnace to provide Al in growing the multiple quantum well structure x Ga 1-x The Al source furnace is utilized to provide Al for growing the multi-quantum well structure x Ga 1-x The As layer requires a beam of aluminum molecules.
2. The method of molecular beam epitaxy growth of a qwi p device according to claim 1, wherein in calculating the relative standard deviation, a plurality of different positions on the substrate support plate are selected as follows:
selecting one or more polar paths in the polar coordinate system, selecting a plurality of polar angles at equal intervals in the range of 0 to 2 pi for each of the one or more polar paths, taking the corresponding positions of coordinates formed by the selected polar paths and polar angles on the substrate supporting plate as the plurality of different positions, wherein any one of the one or more polar paths ρ satisfies the following range: 0<ρ<r 0 Wherein r is 0 Representing the radius of the substrate pallet.
3. The molecular beam epitaxy growth method of qwi p device according to claim 2, wherein for each of the one or more polar paths, the value of polar angle is: 0. pi/6, pi/3, pi/2, 2 pi/3, 5 pi/6, pi, 7 pi/6, 4 pi/3, 3 pi/2, 5 pi/3, 11 pi/6.
4. A molecular beam epitaxy growth method of qwi p device according to claim 2 or 3, characterized in that the number of selected polar diameters is 1 and the polar diameter is equal to r 0 /2。
5. The molecular beam epitaxy growth method of qwi p device according to claim 1, wherein V Ga1 The selection modes of the plurality of different values are as follows: at 0 to V Ga Within a range of 0.05 ∙ V Ga Will be from 0.05 ∙ V for step size Ga To 0.95 and ∙ V Ga Is taken as the V Ga1 Is a plurality of different values.
6. The method of molecular beam epitaxy growth of qwi p device according to claim 1, wherein the thickness H of barrier layer in the multiple quantum well structure B In the range of 40nm<H B <Thickness H of well layer in the multi-quantum well structure of 60nm W In the range of 4nm<H W <6nm。
7. The method of molecular beam epitaxy growth of qwi p device according to claim 6, wherein the number n of periods of barrier layer/well layer in the multiple quantum well structure is in a range of 20<n<60。
8. The molecular beam epitaxy growth method of qwi p device according to claim 1, wherein Al x Ga 1- x The component x in the As layer ranges from 0.2<x<0.5, the average beam velocity V Al The range of (2) is: 0.1 Mu m/h<V Al <0.5 μm/h。
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