CN113972292B - InP-based band gap adjustable structure and photoelectric conversion device - Google Patents
InP-based band gap adjustable structure and photoelectric conversion device Download PDFInfo
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Abstract
The invention discloses an InP-based band gap adjustable structure, which comprises an upper electrode layer, a superlattice functional layer, a lower electrode layer and an InP substrate which are sequentially stacked, wherein the superlattice functional layer is used as an absorption or emission area of light of a photoelectric conversion device, and the superlattice functional layer is a superlattice formed by alternately stacking and growing semiconductor layers with lattice constants larger than and smaller than that of the InP substrate. The invention also discloses a photoelectric conversion device based on the structure and a molecular beam epitaxial growth method of the structure. Due to the method of strain compensation inside the superlattice, two semiconductor materials with large mismatch are integrated together, and factors such as quality degradation of the superlattice and dark current of a device caused by dislocation defects generated by mismatch strain do not need to be considered. Meanwhile, the optical band gap of the strain compensation short-period superlattice can be changed by changing the period length of the short-period superlattice, the photoelectric conversion response wavelength range of the structure is expanded, and the photoelectric conversion device in the near infrared band can realize a wide adjustable response range in the same material system.
Description
Technical Field
The invention relates to an InP-based band gap adjustable structure, a photoelectric conversion device based on the structure and a molecular beam epitaxial growth method, and belongs to the field of semiconductor infrared photoelectric conversion device materials and the field of semiconductor material manufacturing.
Background
Based on InP matrixThe photoelectric conversion device such as an infrared detector generally adopts a semiconductor material such as a random alloy InAlAs, inGaAs, gaAsSb, alAsSb with a sufficient thickness as an absorption region of the device, and when the ternary mixed alloy is matched with an InP substrate lattice, the mass fraction of the corresponding element is determined according to the Vigard law of lattice constant, as follows: in (In) 0.48 Al 0.52 As，In 0.53 Ga 0.47 As，GaAs 0.5 Sb 0.5 ，AlAs 0.55 Sb 0.45 Thus resulting in a fixed operating band for these photoelectric conversion devices with random alloy as the active region. Many researches have been conducted to expand the working band of the InP-based system to the infrared and visible light bands by adjusting the components in the above alloy, but the expansion of the working band by changing the components inevitably introduces mismatch strain into the alloy thin film and the substrate, so that mismatch dislocation is generated at the interface of the substrate and the random alloy thin film, resulting in deterioration of the crystal quality of the random alloy thin film and further affecting the device performance.
Thus, the above random alloy is substantially fixed in the operating band of the photoelectric conversion device while satisfying lattice matching, which also limits the application of InP-based photoelectric conversion devices in other near infrared bands than the operating band determined by the random alloy.
Disclosure of Invention
In order to overcome the defects of the technology, the invention provides an InP-based band gap adjustable structure, a photoelectric conversion device and a preparation method of a strain compensation short-period superlattice.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an InP-based band gap adjustable structure, which comprises an upper electrode layer (1), a superlattice functional layer (2), a lower electrode layer (3) and an InP substrate (4) which are sequentially stacked, wherein the superlattice functional layer (2) is used as an absorption or emission area of light of a photoelectric conversion device, and the superlattice functional layer (2) is a superlattice formed by alternately stacking and growing semiconductor layers with lattice constants larger than and smaller than that of the InP substrate.
In a preferred embodiment of the present invention, the semiconductor layer having a lattice constant larger and smaller than that of the InP substrate (4) is a binary compound or a multicomponent compound composed of group VA and group IIIA elements.
In some embodiments of the invention, the binary compound having a lattice constant greater than that of the InP substrate (4) includes InAs, gaSb, alSb, inSb, and the binary compound having a lattice constant less than that of the InP substrate (4) includes AlAs and GaAs.
In some embodiments of the invention, the multipole compound having a lattice constant greater than that of InP substrate (4) consists of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs and the multipole compound having a lattice constant less than that of InP substrate (4) consists of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs.
In some embodiments of the present invention, each semiconductor layer in a superlattice single period of the superlattice functional layer (2) has a thickness of n ML, where ML (mol layer) is a unit of length and is equal to half of InP lattice constant, and n ranges from 1 to 10.
In some embodiments of the present invention, the superlattice period number of the superlattice functional layer (2) is between 1 and 1000.
In some embodiments of the invention, the superlattice functionality layer (2) is grown epitaxially. In a preferred embodiment of the present invention, the superlattice functional layer (2) is grown at a temperature of 300-600 ℃ and a background vacuum of 1×10 -7 ~1× 10 -10 torr, the growth rate is 0.1-1 μm/h.
In some embodiments of the invention, the upper electrode layer (1) and the lower electrode layer (2) are artificially doped semiconductor layers, including n-type and p-type doped semiconductor layers, and the doping sources include Si, te, be, and C.
On the other hand, the invention provides a method for preparing an InP-based band gap adjustable structure, which adopts an epitaxial method to sequentially epitaxially grow a lower electrode layer (3), a superlattice functional layer (2) and an upper electrode layer (1) on an InP substrate (4) to form a strain compensation short-period superlattice epitaxial structure.
The invention also provides a photoelectric conversion device structure which comprises a bottom electrode, a structure (comprising an InP substrate, a lower electrode layer, a superlattice functional layer and an upper electrode layer) based on the InP-based band gap and a top electrode, wherein an ohmic structure is formed between the bottom electrode and the lower electrode layer, ohmic contact is formed between the upper electrode layer and the top electrode, the photoelectric conversion device can realize the detection and luminous functions of near infrared light to mid infrared light, and the response wavelength range of the device is adjustable.
The beneficial effects are that:
the InP-based strain compensation short-period superlattice provided by the invention has an adjustable band gap, the thickness of each layer of the short-period superlattice can be precisely controlled through a molecular beam epitaxy device, and the strain compensation condition is met, so that the InP-based strain compensation short-period superlattice and the upper electrode layer and the lower electrode layer have higher crystal quality. And the increase of the period length of the strain compensation short-period superlattice can lead the band gap of the short-period superlattice to be smaller than the band gap of the multi-element random alloy corresponding to the same component, which can lead the working band of the detector to be expanded towards the long wavelength direction, and simultaneously ensure the crystal quality of the short-period superlattice and the performance of the strain compensation short-period superlattice photoelectric conversion device.
Drawings
Fig. 1 is a schematic diagram of an InP-based bandgap tunable structure according to the present invention.
Fig. 2 is a schematic structural diagram of a photoelectric conversion device based on an InP-based bandgap-tunable structure in the present invention.
Fig. 3 is a schematic diagram of the structure of the strain compensated InAs/AlAs short period superlattice of different period lengths (left) and X-ray diffraction pattern (right) in example 1 of the present invention.
Fig. 4 is an atomic force microscope image of strain compensated InAs/AlAs short period superlattice of different period lengths in example 1 of the present invention.
Fig. 5 is a graph of the ambient photoluminescence of strain-compensated InAs/AlAs short-period superlattice of varying period lengths in example 1 of the invention.
Fig. 6 is a room temperature fourier transform infrared spectrum of a strain compensated InAs/AlAs short period superlattice of varying period lengths in example 1 of the present invention.
Fig. 7 is a schematic diagram of the structure of the strain compensated InAs/GaAs short period superlattice of various period lengths (left) and X-ray diffraction pattern (right) in example 2 of the present invention.
Fig. 8 is a graph showing the wave functions and distribution of one-dimensional electron and hole and one-dimensional energy bands calculated by the strain compensated InAs/GaAs short period superlattice of different period lengths in example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings.
The invention provides an InP-based band gap adjustable strain compensation short-period superlattice structure (shown in figure 1) and a preparation method of the strain compensation short-period superlattice, wherein the strain compensation short-period superlattice structure comprises an InP substrate (4), a lower electrode layer (3), a superlattice functional layer (2) and an upper electrode layer (1), and a specific epitaxial structure is shown in figure 1.
In the present invention, the orientation of the InP substrate (4) is preferably selected to be (001), and the polishing type of the substrate includes single-sided polishing and double-sided polishing, and preferably the substrate polishing type is double-sided polishing. The electrical types of the substrate comprise a conductive substrate and a semi-insulating substrate, preferably the electrical type of the substrate is a conductive substrate, the conductive type of the substrate comprises an n type and a p type, and the specific substrate conductive type is selected according to the processing, the function and the application scene of the photoelectric conversion device manufactured based on the epitaxial structure.
In the invention, the superlattice functional layer (2) is a superlattice formed by alternately stacking and growing two extremely thin semiconductor layers with lattice constants larger than and smaller than that of InP. Preferably, the semiconductor layers having lattice constants greater than and less than InP lattice constants are binary or multi-component compounds of group VA and group IIIA elements. Wherein the binary compound semiconductor material with a lattice constant larger than InP comprises InAs, gaSb, alSb and InSb, and the binary compound semiconductor material with a lattice constant smaller than InP comprises GaAs and AlAs; the multi-compound semiconductor material having a lattice constant larger than InP is composed of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs, and the multi-compound semiconductor material having a lattice constant smaller than InP is composed of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs. The superlattice functional layer is formed by selecting one of the above material larger than InP lattice constant and the material smaller than InP lattice constant, and then alternately stacking and growing the two semiconductor materials with the thickness of an integer number of atomic layers (ML), wherein the thicknesses of the two semiconductor layers are m ML and n ML, such as InAs (m ML)/AlAs (n ML), inAs (m ML)/GaAs (n ML), gaSb (m ML)/GaAs (n ML), alSb (m ML)/AlAs (n ML), inSb (m ML)/GaAs (n ML), inSb (m ML)/AlAs (n ML), wherein ML (monolayer) is a length unit and is equal to half of InP lattice constant, the range of m and n is 1 to 10, and the period length of the strain compensating short period superlattice is equal to (m+n) ML. And the effective band gap of the strain compensation short-period superlattice can be changed along with the change of the period length of the superlattice, so that the band gap adjusting function is realized. Preferably, the superlattice period number of the superlattice functional layer (2) is between 1 and 1000, and the range can enable the thickness of the superlattice functional layer (2) to be suitable, and the superlattice functional layer has high quantum efficiency. The superlattice functional layer (2) integrates two ultrathin semiconductor material films with different band gaps and different lattice constants to obtain different optical band gaps, and realizes the function of adjusting response wave bands, thereby being applicable to absorption or emission of devices at different wavelengths. Due to the method of strain compensation inside the superlattice, two semiconductor materials with large mismatch are integrated together, and factors such as quality degradation of the superlattice and dark current of a device caused by dislocation defects generated by mismatch strain do not need to be considered. Meanwhile, the optical band gap of the strain compensation short-period superlattice can be changed by changing the period length of the short-period superlattice, the photoelectric conversion response wavelength range of the structure is expanded, and the photoelectric conversion device in the near infrared band can realize a wide adjustable response range in the same material system.
In the invention, the superlattice functional layer (2) is obtained by epitaxial growth, so that the cycle length is regulated and controlled more accurately. The superlattice functional layer (2) is formed by adopting a low-temperature molecular beam epitaxy method, and the speed or the beam current ratio of elements in the VA group and the IIIA group needs to be controlled. In particular, epitaxial strainThe growth temperature of the compensating short period superlattice is 300-600 ℃, the semiconductor film with the lattice constant smaller than that of the InP substrate is preferentially grown, the actual growth temperature depends on the length of a single period of the superlattice, the rate ratio of VA group elements to IIIA group elements is 1-10, and the background vacuum degree is 1 multiplied by 10 -7 ~1× 10 -10 torr, the growth rate is 0.1-1 μm/h. The epitaxial growth conditions of the superlattice functional layer (2) are very important to the crystal quality of the superlattice functional layer (2), and the crystal quality of the superlattice functional layer (2) can affect the performance of the final device.
The upper electrode layer (1) and the lower electrode layer (3) are artificially doped semiconductor layers, and for devices with InP as a substrate, the preferred material of the electrode layers is In 0.48 Al 0.52 As、In 0.53 Ga 0.47 As、GaAs 0.5 Sb 0.5 、AlAs 0.55 Sb 0.45 Or a multi-compound alloy formed of two or more of the foregoing. The artificially doped semiconductor layer may Be an n-type or p-type doped semiconductor layer, the doping sources include Si, te, be and C, and the appropriate doping sources are selected so that the doped semiconductor layer can effectively conduct out unbalanced carriers generated by the superlattice functional layer (2) or conduct carriers into the superlattice functional layer (2) while maintaining crystal quality and surface flatness. The doping amount of the doping source is determined according to the electrode contact barrier but is generally not less than 1×10 18 cm -3 . The materials of the upper electrode layer (1) and the lower electrode layer (3) are selected according to the principle that the band gap is larger than that of the superlattice functional layer and the lattice constant is matched with the InP substrate, and the performance of a device manufactured based on the epitaxial structure is not deteriorated due to the problems of lattice quality and the like of the electrode layer under the condition that the electrode layer is matched with the substrate lattice. The upper electrode layer (1) and the lower electrode layer (3) have the function of leading out carriers generated in the strain-compensated short-period superlattice functional layer (2) or leading in carriers to the superlattice functional layer (2) and form ohmic contact with metal wires outside the device.
In the invention, the thickness of each layer in the photoelectric detection device of the strain compensation short period superlattice is not particularly limited, and a proper thickness is selected according to actual needs. Specifically, the thickness of the upper electrode layer (1) and the lower electrode layer (3) is 100-1000 nm.
The structure of the invention can sequentially epitaxially grow the lower electrode layer (3), the superlattice functional layer (2) and the upper electrode layer (1) on the InP substrate (4) by adopting an epitaxial method, so as to form the structure based on InP-based band gap adjustment. Specifically, after deoxidizing the InP substrate (4), epitaxially growing an artificially doped lower electrode layer (3) with a thickness of 100-1000 nm, then changing the substrate temperature to a proper temperature, epitaxially growing a superlattice functional layer (2), and finally changing the substrate temperature to a proper temperature to grow an upper electrode layer (1).
The invention also provides a photoelectric conversion device based on the InP-based band gap adjustable strain compensation short-period superlattice epitaxial structure, which comprises detection and light emitting functions, and the photoelectric conversion device specifically comprises a bottom electrode, an epitaxial structure (comprising an InP substrate, a lower electrode layer, a superlattice functional layer and an upper electrode layer) based on the InP-based band gap adjustable strain compensation short-period superlattice epitaxial structure and a top electrode, wherein ohmic contact is formed between the bottom electrode and the lower electrode layer, and ohmic contact is formed between the upper electrode layer and the top electrode. The photoelectric conversion device can realize near infrared to mid infrared detection and luminescence functions through the band gap adjustable function of the epitaxial structure.
In the present invention, the specific operation modes of the vapor deposition method of the bottom electrode and the top electrode and the process method of mesa etching of the strain compensation short period superlattice photoelectric device are not particularly limited, and modes well known to those skilled in the art may be adopted.
The strain-compensated short-period superlattice has reliable epitaxial structure quality, can be widely applied to absorption areas of photoelectric detection devices such as PIN detectors, avalanche photodiodes and the like and active areas of light-emitting devices, and realizes adjustability of response range of the devices.
The following description of the embodiments of the present invention will be made with reference to embodiments of the present invention, which are only some, but not all, of which InAs/AlAs and InAs/GaAs strain compensating short period superlattices can be experimentally and theoretically tunable. All other implementations, which can be made by those skilled in the art without the benefit of the teachings of this invention, are intended to be within the scope of this invention.
Example 1:
InP-based InAs/AlAs strain compensated short period superlattice epitaxial structures. The specific scheme is as follows:
the band gap of the InAlAs ternary random alloy is larger than that of the InAs/AlAs strain compensation short-period superlattice, so that InAlAs is selected as semiconductor materials of an upper electrode layer and a lower electrode layer of the InAs/AlAs short-period superlattice.
(1) Carrying out deoxidization treatment on an InP (001) substrate in an arsenic atmosphere for 15min, wherein the deoxidization temperature is 520-540 ℃;
(2) Epitaxy buffer layer by molecular beam epitaxy method with background vacuum degree of 1×10 -7 ~1× 10 -8 Epitaxial InAlAs random alloy semiconductor material at torr and 490 ℃ with thickness of 100nm and growth rate of 0.9 mu m/h;
(3) The short-period superlattice with the epitaxial strain compensation is adopted, the temperature of the obtained material is reduced to below 450 ℃ at the temperature reduction rate of 30 ℃ per minute, and the InAs/AlAs short-period superlattice with the epitaxial thickness of 250 nm is adopted on the lower electrode layer by adopting a molecular beam epitaxy method;
fig. 3 is an X-ray diffraction pattern and corresponding structure diagram of an InAs/AlAs strain compensated short period superlattice of the same thickness at different period lengths in accordance with example 1 of the present invention. As can be seen from FIG. 3, the InAs/AlAs short period superlattice with different period lengths has better crystal quality, and satellite peaks in the X-ray diffraction diagram indicate that the InAs/AlAs short period superlattice has better periodicity along the growth direction, and the InAs semiconductor layer and the AlAs semiconductor layer have better interfaces.
Fig. 4 is an atomic force microscope image of an InAs/AlAs strain compensated short period superlattice of the same thickness at different period lengths in example 1 of the present invention. It can be seen from fig. 4 that the InAs/AlAs short-period superlattice with different period lengths has a flat surface, and the root mean square roughness of the surface is lower than 1nm.
Fig. 5 is a photoluminescence spectrum of an InAs/AlAs strain compensated short period superlattice of different period lengths in example 1 of the present invention. As can be seen from fig. 5, the bandgap of the InAs/AlAs short-period superlattice is smaller than the bandgap of the inaias random alloy and is tunable in the 880-1280 nm band range, and the bandgap of the InAs/AlAs superlattice decreases as the period length of the strain-compensated short-period superlattice increases. Therefore, the InAlAs/AlAs short period superlattice expands the wavelength of the InAlAs ternary random alloy, can realize the red shift of detection wavelength, and is continuously adjustable.
Fig. 6 is a reflection fourier transform infrared spectrum of an InAs/AlAs strain compensated short period superlattice of different period lengths in example 1 of the present invention. As can be seen from fig. 6, long wavelength absorption occurs near the absorption edge of the InP substrate and the bandgap of the InAs/AlAs superlattice decreases as the period length of the strain-compensated short period superlattice increases. It was thus determined that the InAs/AlAs short period superlattice exhibited longer wavelength absorption relative to the inaias random alloy.
Example 2:
InP-based InAs/GaAs strain-compensated short-period superlattice epitaxial structures. The specific scheme is as follows:
the InAlAs ternary random alloy band gap is larger than that of the InAs/GaAs strain compensation short period superlattice, so that InAlAs is selected as semiconductor materials of an upper electrode layer and a lower electrode layer of the InAs/GaAs short period superlattice, larger energy band deviation exists between the electrode layer and the strain compensation short period superlattice, and a band gap gradual change layer with a certain thickness is needed between the electrode layer and the strain compensation short period superlattice in a specific device structure.
(1) Carrying out deoxidization treatment on an InP (001) substrate in an arsenic atmosphere for 15min, wherein the deoxidization temperature is 520-540 ℃;
(2) Epitaxial InAlAs buffer layer with molecular beam epitaxial growth method and background vacuum degree of 1×10 -7 ~1× 10 -8 the thickness of the epitaxial InAlAs random alloy semiconductor material is 100nm under the conditions of torr and 490 ℃ and the growth rate is 0.9 mu m/h;
(3) Epitaxially growing a strain compensation short-period superlattice by a molecular beam epitaxy method, cooling the obtained material to below 450 ℃ at a cooling rate of 30 ℃ per minute, and epitaxially growing an InAs/GaAs strain compensation short-period superlattice with the thickness of 250 nm on the lower electrode layer by the molecular beam epitaxy method;
fig. 7 is a schematic diagram of the structure of the InAs/GaAs strain compensated short period superlattice of various period lengths (left) and X-ray diffraction pattern (right) in example 2 of the present invention. The satellite peaks in the X-ray diffraction diagram of fig. 7 show that the InAs/GaAs short period superlattice has a good periodicity along the growth direction, and the InAs semiconductor layer has a good interface with the GaAs semiconductor layer.
Fig. 8 shows one-dimensional band information and one-dimensional electron and hole wave functions and distributions thereof calculated from the InAs/GaAs strain compensated short period superlattice of different period lengths in example 2 of the present invention. As can be seen from fig. 8, as the period length of the InAs/GaAs strain compensating short-period superlattice increases, the bandgap of the InAs/GaAs short-period superlattice gradually decreases, so that the operating band of the InAs/GaAs short-period superlattice can exceed the upper limit 1670nm of the absorption wavelength of the InGaAs random alloy, and can even reach a 2 μm band.
The foregoing is merely illustrative of the preferred embodiments of this invention, and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of the invention, and such variations and modifications are to be regarded as being within the scope of the invention.
Claims (11)
1. The structure based on the InP-based band gap is characterized by comprising an upper electrode layer (1), a superlattice functional layer (2), a lower electrode layer (3) and an InP substrate (4) which are sequentially stacked, wherein the superlattice functional layer (2) is used as an absorption or emission area of light of a photoelectric conversion device, and the superlattice functional layer (2) is a superlattice formed by alternately stacking and growing semiconductor layers with lattice constants larger than and smaller than that of the InP substrate (4).
2. The InP-based bandgap tunable structure according to claim 1, wherein the semiconductor layers having lattice constants greater than and less than that of the InP substrate (4) are binary or multicomponent compounds of group VA and group IIIA elements.
3. An InP-based bandgap tunable structure according to claim 2, wherein said binary compound having a lattice constant larger than that of said InP substrate (4) comprises InAs, gaSb, alSb, inSb and said binary compound having a lattice constant smaller than that of said InP substrate (4) comprises AlAs and GaAs.
4. The InP-based bandgap tunable structure according to claim 2, wherein the multi-compound having a lattice constant larger than that of the InP substrate (4) consists of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs and the multi-compound having a lattice constant smaller than that of the InP substrate (4) consists of two or more of InAs, gaSb, alSb, inSb, alAs, gaAs.
5. The InP-based bandgap tunable structure according to claim 1, wherein each semiconductor layer in a superlattice single period of the superlattice functional layer (2) has a thickness of n ML, wherein ML (mol layer) is a unit of length and equal to half of the InP lattice constant, and n ranges from 1 to 10.
6. The InP-based bandgap tunable structure according to claim 1, wherein the superlattice number of the superlattice functional layer (2) is between 1 and 1000.
7. InP-based bandgap tunable structure according to claim 1, wherein the superlattice functional layer (2) is grown epitaxially.
8. The InP-based bandgap tunable structure according to claim 7, wherein the superlattice functional layer (2) has a growth temperature of 300-600 ℃ and a background vacuum of 1 x 10 -7 ~1× 10 -10 torr, the growth rate is 0.1-1 μm/h.
9. InP-based bandgap tunable structure according to claim 1, wherein the upper electrode layer (1) and the lower electrode layer (3) are artificially doped semiconductor layers comprising n-type and p-type doped semiconductor layers, the doping sources of the artificially doped semiconductor layers comprising Si, te, be and C.
10. A method of preparing an InP-based bandgap tunable structure according to any one of claims 1 to 9, wherein the lower electrode layer (3), the superlattice functional layer (2) and the upper electrode layer (1) are epitaxially grown sequentially on the InP substrate (4) using an epitaxial process to form a strain-compensated short-period superlattice epitaxial structure.
11. A photoelectric conversion device structure, characterized by comprising a bottom electrode, the InP-based band gap-adjustable structure of any one of claims 1 to 9, and a top electrode, wherein ohmic contact is formed between the bottom electrode and the lower electrode layer (3), ohmic contact is formed between the upper electrode layer (1) and the top electrode, and the photoelectric conversion device can realize near-infrared to mid-infrared detection and luminescence functions, and has an adjustable response wavelength range.
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