CN112201722B - Multi-band detection structure and manufacturing method thereof - Google Patents
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- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
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Abstract
The inventionA multi-band detection structure is disclosed, comprising a substrate and a nanowire array formed on the substrate, the nanowire array comprising at least: a first semiconductor nanowire of one-dimensional structure having a first absorption wavelength; the second semiconductor nanowire with the one-dimensional structure has a second absorption wavelength, the first absorption wavelength is different from the second absorption wavelength, and the first semiconductor nanowire and the second semiconductor nanowire are arranged in parallel. The invention also discloses a manufacturing method of the multiband detection structure, wherein the first semiconductor nanowire or the second semiconductor nanowire is epitaxially grown on the surface of the substrate under the action of the catalyst. The invention realizes the beta-Ga by means of a double-layer mask2O3And transverse distribution array integration of GaAs material nanowires, high-quality monolithic integration of heterogeneous materials is realized by utilizing the stress release characteristic of the nanowires in two-dimensional directions, and the light absorption rate is improved by utilizing the light trap effect of the nanowire arrays, so that device structure support is provided for research, development and preparation of high-performance multiband photodetectors.
Description
Technical Field
The invention belongs to the technical field of optoelectronic devices, and particularly relates to a multiband detection structure and a manufacturing method thereof.
Background
Infrared light is an electromagnetic wave with a wavelength between that of visible light and terahertz waves, and generally divides the infrared spectrum into three regions: a near infrared region (0.75 to 2.5 μm), a mid-infrared region (2.5 to 25 μm) and a far infrared region (25 to 300 μm). Generally, the near infrared spectrum is generated by frequency doubling and frequency combining of molecules; the mid-infrared spectrum belongs to the fundamental frequency vibration spectrum of molecules; the far infrared spectrum belongs to the rotation spectrum of molecules and the vibration spectrum of some groups. The infrared detector converts the infrared light signal into some measurable physical quantity, thereby realizing perception. Objects in the earth's temperature environment have infrared radiation as long as they are not at absolute zero. Therefore, infrared is of particular importance for target detection in the earth environment. Compared with other means, the infrared detection has the characteristics of strong concealment, small adverse weather influence, suitability for night use and strong target identification capability, and is widely applied to the fields of meteorological prediction, ground imaging, military reconnaissance, environmental monitoring, safety inspection and the like.
The wavelength range of the ultraviolet light is 10-380 nm, and the ultraviolet light is divided into two sections. Ultraviolet light with the wavelength of 10-200 nm can be absorbed by nitrogen, oxygen, carbon dioxide and water in the air, so that research can be carried out only in vacuum, and the corresponding spectral range is called as a vacuum ultraviolet band. Ultraviolet rays with the wavelength of 200-280 nm are absorbed by an ozone layer when passing through the stratosphere on the earth surface and cannot reach the earth surface, a corresponding spectral range is called a solar blind ultraviolet band, and a corresponding optical detector is called a solar blind ultraviolet detector. On the earth surface, the solar blind ultraviolet detector is not interfered by sunlight, has high sensitivity and can accurately detect light in any environment, so the solar blind ultraviolet detector is widely applied to military and civil fields. In military affairs, missile early warning can be carried out according to solar blind ultraviolet signals emitted by missile tail flames, and compared with infrared detection, the target detection accuracy rate is higher. In civil use, the method is widely applied to the aspects of medical sterilization, flame detection, electric arc detection, ozone cavity detection and other environment detection.
In conclusion, solar blind ultraviolet detection and infrared detection have advantages and disadvantages in earth environment application, and the preparation of the double-color detector combined with two detection technologies has great scientific research value and application potential.
β-Ga2O3The material is a direct band gap, the forbidden band width is about 4.9eV, the absorption peak (253 nm) of the material is in a solar blind ultraviolet band, and the material is a transparent material in a visible light band, so the material has great application potential in the solar blind ultraviolet detection aspect. The energy gap of GaAs material is about 1.424eV, the absorption peak (-871 nm) is in near infrared band, and the absorption wavelength of its homologous InGaAs and InAs material can be further extended to 3.54 μm toward middle infrared band. By integrating beta-Ga on the same substrate2O3And the GaAs series material can realize the preparation of the ultraviolet and infrared double-color detector.
In the prior art, a scheme for realizing a two-color detector based on a traditional film structure comprises multilayer film stack epitaxy and mask partition secondary epitaxy, but the problem of lattice mismatch is inevitable generally in material integration based on a simple substance semiconductor or a binary/ternary compound semiconductor material, the performance of a photoelectric device is seriously affected by stress introduced by lattice mismatch and dislocation along with the stress, and the problem of difficult epitaxy control exists in a quaternary compound with higher controllability.
Disclosure of Invention
An embodiment of the present invention provides a multiband detection structure and a method for manufacturing the same, for solving the problem of lattice mismatch in the prior art, including:
in one embodiment, a multi-band detection structure includes a substrate and a nanowire array formed on the substrate, the nanowire array including at least:
a first semiconductor nanowire of one-dimensional structure having a first absorption wavelength;
the second semiconductor nanowire with the one-dimensional structure has a second absorption wavelength, the first absorption wavelength is different from the second absorption wavelength, and the first semiconductor nanowire and the second semiconductor nanowire are arranged in parallel.
In one embodiment, a method for fabricating a multi-band detection structure is provided, which includes:
(1) depositing a first mask on the surface of the substrate, and forming a first catalyst hole on the first mask;
(2) depositing a first catalyst in the first catalyst pores;
(3) depositing a second mask on the surface of the first mask, and forming a second catalyst hole on the second mask to the surface of the substrate, wherein the second catalyst hole and the first catalyst hole are transversely staggered;
(4) depositing a second catalyst in the second catalyst pores;
(5) epitaxially growing a second semiconductor nanowire under the action of a second catalyst;
(6) removing the second mask and the second catalyst;
(7) and epitaxially growing a first semiconductor nanowire under the action of the first catalyst.
Compared with the prior art, the method realizes the beta-Ga by means of the double-layer mask2O3And GaAs series materialThe method is characterized in that the material nanowire is transversely distributed and arrayed, high-quality monolithic integration of heterogeneous materials is realized by utilizing the stress release characteristic of the nanowire in the two-dimensional direction, and the light absorption rate is improved by utilizing the light trap effect of the nanowire array, so that device structure support is provided for research, development and preparation of a high-performance multiband photodetector.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1a shows the deposition of a first Al layer in example 1 of the present application2O3The structure schematic diagram of the mask and the mask after opening holes;
FIG. 1b shows a top view of FIG. 1 a;
FIG. 2a shows the deposition of a second SiO layer in example 1 of the present application2A structure schematic diagram after a mask and deposition of Ga liquid drops;
FIG. 2b shows a top view of FIG. 2 a;
FIG. 3a is the epitaxy of β -Ga in example 1 of the present application2O3A schematic structure diagram after nanowire array;
FIG. 3b shows a top view of FIG. 3 a;
FIG. 4a shows the removal of SiO in the upper layer of the film in example 1 of the present application2Thin film and beta-Ga2O3Schematic structural diagram of Ga liquid drop at the top end of the nanowire;
FIG. 4b shows a top view of FIG. 4 a;
FIG. 5a is a schematic structural diagram of the GaAs nanowire grown in the embodiment 1 of the present application;
FIG. 5b shows a top view of FIG. 5 a;
fig. 6 is a top view of an epitaxial structure in embodiment 2 of the present application;
FIG. 7 is a top view of an epitaxial structure in example 3 of the present application;
FIG. 8 is a top view of an epitaxial structure in example 4 of the present application;
fig. 9 is a top view of an epitaxial structure in example 5 of the present application.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In an embodiment of the present application, as shown in fig. 5a, a multiband detection structure is provided, which includes a substrate 1 and a nanowire array formed on the substrate, the nanowire array including at least:
a first semiconductor nanowire 2 of one-dimensional structure having a first absorption wavelength;
the second semiconductor nanowire 3 with the one-dimensional structure has a second absorption wavelength, the first absorption wavelength is different from the second absorption wavelength, and the first semiconductor nanowire and the second semiconductor nanowire are arranged in parallel.
In one embodiment, the multi-band detection structure is an infrared/ultraviolet dual color detection structure, wherein:
the first semiconductor nanowire is made of an infrared absorption material. In a preferred embodiment, the first semiconductor nanowire is made of a GaAs material, preferably InGaAs or InAs material;
the second semiconductor nanowire is made of an ultraviolet absorption material. In a preferred embodiment, the second semiconductor nanowire is beta-Ga2O3A material.
The first semiconductor nanowire 2 and the second semiconductor nanowire 3 are vertically grown on the surface of the substrate.
In other embodiments, the multiband detection structure may be other multi-color or multiband detection structures, such as nanowires for absorbing three different wavelength bands, which may be grown on the substrate in parallel for three colors, or multiple nanowires for the same color but different wavelength band intervals.
In one embodiment, the substrate is a sapphire insulating substrate.
In another embodiment, a method for fabricating a multiband detection structure is provided, including:
(1) depositing a first mask on the surface of the substrate, and forming a first catalyst hole on the first mask;
(2) depositing a first catalyst in the first catalyst pores;
(3) depositing a second mask on the surface of the first mask, and forming a second catalyst hole in the second mask, wherein the second catalyst hole and the first catalyst hole are transversely staggered;
(4) depositing a second catalyst in the second catalyst pores;
(5) epitaxially growing a second semiconductor nanowire under the action of a second catalyst;
(6) removing the second mask and the second catalyst;
(7) and epitaxially growing a first semiconductor nanowire under the action of the first catalyst.
In one embodiment, the first mask is Al2O3The first catalyst is Au particles or In liquid drops, and the first semiconductor nanowire is an InGaAs nanowire.
In one embodiment, the second mask is SiO2A mask, the second catalyst is Ga liquid drop, and the second semiconductor nanowire is beta-Ga2O3A nanowire.
In summary, the two-color detector based on the nanowire structure further has a single-wire axial/radial integration implementation scheme, compared with single-wire integration, the integration materials are separated in the transverse distribution array integration scheme, the limitation of interface potential barriers on a serial interface on carrier transport is avoided, and meanwhile, the light receiving types can be simply distinguished through array addressing. In addition, the problem of bending of heterogeneous interface nanowires in common catalytic epitaxy can be avoided by avoiding single-wire integration. In the above, the laterally distributed array integration scheme has advantages over single line integration in terms of device operation mechanism and process implementation.
Example 1
Referring to FIG. 5a, the ultraviolet/infrared double-color detecting structure comprises a substrate 1 and beta-Ga vertically grown on the surface of the substrate 12O3Nanowire arrays 3 and InGaAs nanowire arrays 2.
Aligned beta-Ga as shown in connection with FIG. 5b2O3The nanowires and the InGaAs nanowires in columns are arranged in a staggered mode along the transverse direction.
The manufacturing process of the ultraviolet/infrared double-color detection structure comprises the following steps:
1) first layer mask deposition and catalyst positioning preparation
a) With reference to FIGS. 1a and 1b, a first layer of Al is deposited on a substrate 12O3A mask 4 with a thickness of about 20 nm;
b) applying photoresist to the first layer of Al2O3The mask 4 is subjected to mask opening 41, and then the positioning deposition of the Au thin film 5 is realized by using a to-be-glued stripping technology.
2) Second layer mask deposition
a) Depositing a second layer of SiO, as shown in conjunction with FIGS. 2a and 2b2A mask 6 with a thickness of about 30 nm;
b) the deposited bilayer mask is opened 61 with photoresist.
3) Nanowire epitaxy
a) The substrate is sent into a gallium oxide MOCVD reaction chamber, and Ga liquid drops 7 are deposited to be used as a catalyst;
b) epitaxy of beta-Ga by the catalytic action of Ga droplets 7, as shown in connection with FIGS. 3a and 3b2O3 A nanowire array 3;
c) as shown in the combination of FIG. 4a and FIG. 4b, the sample is taken out of the MOCVD chamber, and the upper SiO layer is removed by BOE wet etching2Thin film and beta-Ga2O3Ga drops on top of nanowires to make the lower layer Al2O3Exposing the mask and the Au film;
d) as shown in fig. 5a and 5b, the substrate is sent to GaAs MOCVD equipment to anneal the Au thin film to form Au catalytic particles, and GaAs nanowires 2 are grown by using the catalytic properties of the Au particles;
4) catalyst, mask removal and electrodeposition
The catalyst and mask may be selected to remain according to the electrodeposition process design.
Example 2
In this example, the epitaxial structure was ordered array cross-batch epitaxy, beta-Ga2O3The nanowire 3 and the InGaAs nanowire 2 are arranged in a crossed mode.
The manufacturing method of the corresponding cross array integrated structure can also be realized by directly coating a plurality of catalysts to continuously carry out twice epitaxy by utilizing the single catalytic action of the catalysts in different epitaxy processes.
Example 3
In this embodiment, the epitaxial structure adopts an ordered array function to differentiate batch epitaxy.
Example 4
In this embodiment, the epitaxial structure employs ordered array cross batch epitaxy — local array.
Example 5
In this embodiment, the epitaxy structures adopt random array functions to differentiate batch epitaxy.
Corresponding to the random array function partition structure, the manufacturing method can be realized by depositing two or more catalysts at different positions by using step masks and then continuously performing twice epitaxy by using single catalytic action of the catalysts in different epitaxy processes under the condition of no mask or exposing multiple catalysts by using a single mask.
In addition, the detector structure provided by the invention can be realized by using selective area etching after deposition and selective area secondary epitaxy.
The material epitaxial equipment of the invention is not limited to MOCVD, and also comprises HVPE, CVD or PVD equipment and the like which are commonly used for nanowire catalytic epitaxy or uncatalyzed epitaxy.
The advantages of the invention at least include:
1) the nanowire can effectively and reliably release stress in a transverse two-dimensional direction by virtue of one-dimensional structural characteristics of the nanowire, and dislocation-free material integration can be realized by controlling the diameter of the nanowire;
2) the light trapping effect specific to the characteristics of the nanowire array can increase the light absorption rate;
3) the device operation mechanism is as follows: the integrated materials are separated in space, the limitation of interface potential barriers on a serial interface on carrier transport is avoided, and meanwhile, the light receiving types can be simply distinguished through array addressing.
4) The preparation process comprises the following steps: the integrated materials are separated spatially, so that the problem of bending of heterogeneous interface nanowires in common catalytic epitaxy and the problem of limitation of the thickness of a shell layer in a core-shell structure can be avoided.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
In the present aspects, where an element or component is referred to as being included in and/or selected from a list of recited elements or components, it is understood that the element or component can be any one of the recited elements or components and can be selected from a group consisting of two or more of the recited elements or components. Moreover, it should be understood that elements and/or features of the compositions, apparatus, or methods described herein may be combined in various ways, whether explicitly described or implicitly described herein, without departing from the spirit and scope of the present teachings.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. Furthermore, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. In addition, where the term "about" is used before a quantity, the present teachings also include the particular quantity itself unless specifically stated otherwise.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
It is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for purposes of clarity, other elements. However, those skilled in the art will recognize that these and other elements may be desirable. However, because such elements are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements is not provided herein. It should be understood that the figures are presented for illustrative purposes and not as construction diagrams. The omission of details and modifications or alternative embodiments is within the scope of one skilled in the art.
It is to be understood that in certain aspects of the invention, a single component may be replaced by multiple components and that multiple components may be replaced by a single component to provide an element or structure or to perform a given function or functions. Except where such substitution would not operate to practice a particular embodiment of the invention, such substitution is considered within the scope of the invention.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (7)
1. A method of fabricating a multiband detection structure, the multiband detection structure comprising a substrate and a nanowire array formed thereon, the nanowire array comprising:
a first semiconductor nanowire of one-dimensional structure having a first absorption wavelength;
the second semiconductor nanowire with the one-dimensional structure has a second absorption wavelength, the first absorption wavelength is different from the second absorption wavelength, and the first semiconductor nanowire and the second semiconductor nanowire are arranged in parallel;
the manufacturing method comprises the following steps:
(1) depositing a first mask on the surface of the substrate, and forming a first catalyst hole on the first mask;
(2) depositing a first catalyst within the first catalyst pores;
(3) depositing a second mask on the surface of the first mask, and forming a second catalyst hole on the second mask to the surface of the substrate, wherein the second catalyst hole and the first catalyst hole are transversely staggered;
(4) depositing a second catalyst within the second catalyst pores;
(5) epitaxially growing a second semiconductor nanowire under the action of a second catalyst;
(6) removing the second mask and the second catalyst;
(7) and epitaxially growing a first semiconductor nanowire under the action of the first catalyst.
2. The method of manufacturing according to claim 1, wherein: the first semiconductor nanowire is made of an infrared absorption material.
3. The method of manufacturing according to claim 2, wherein: the first semiconductor nanowire is made of InGaAs or InAs material.
4. The method of manufacturing according to claim 1, wherein: the second semiconductor nanowire is made of an ultraviolet absorption material.
5. The method of manufacturing according to claim 1, wherein: the first semiconductor nanowire or the second semiconductor nanowire is vertically grown on the surface of the substrate.
6. The method of claim 1, wherein the first mask is Al2O3And masking, wherein the first catalyst is Au particles or In droplets, and the first semiconductor nanowire is an InGaAs nanowire.
7. Method of manufacturing according to claim 1 or 4, wherein the second mask is SiO2A mask, the second catalyst is Ga liquid drop, and the second semiconductor nanowire is beta-Ga2O3A nanowire.
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