WO2018103647A1 - 基于Ga2O3材料的紫外光电探测器的制备方法 - Google Patents

基于Ga2O3材料的紫外光电探测器的制备方法 Download PDF

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WO2018103647A1
WO2018103647A1 PCT/CN2017/114675 CN2017114675W WO2018103647A1 WO 2018103647 A1 WO2018103647 A1 WO 2018103647A1 CN 2017114675 W CN2017114675 W CN 2017114675W WO 2018103647 A1 WO2018103647 A1 WO 2018103647A1
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layer
substrate
sputtering
forming
gas
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PCT/CN2017/114675
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English (en)
French (fr)
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贾仁需
元磊
张弘鹏
张玉明
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西安电子科技大学
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Priority claimed from CN201611124463.4A external-priority patent/CN106409987B/zh
Priority claimed from CN201611124461.5A external-priority patent/CN106449894B/zh
Application filed by 西安电子科技大学 filed Critical 西安电子科技大学
Publication of WO2018103647A1 publication Critical patent/WO2018103647A1/zh
Priority to US16/119,067 priority Critical patent/US10629766B2/en

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Definitions

  • the invention belongs to the field of integrated circuit technology, and in particular relates to a method for preparing an ultraviolet photodetector based on a Ga 2 O 3 material.
  • Avalanche Photo Diode (APD) detectors and photodetection diodes are PN junction type photodetection diodes that use the avalanche multiplication effect of carriers to amplify optical signals to improve detection sensitivity.
  • the ultraviolet to infrared light region has great use value in the development of military high-tech and civilian products market, such as real-time detection or effective tracking of flying targets that can release a large amount of ultraviolet radiation in tail smoke or plume in the blind spot.
  • the current APD detector does not have extremely high pressure resistance and puncture resistance, it is not suitable for applications in extreme environments such as high frequency, high radiation, high temperature and high pressure.
  • photodetection diodes still have problems such as weak light absorption capability and weak ability in ultraviolet light detection.
  • the present invention provides a method for preparing an ultraviolet photodetector based on a Ga 2 O 3 material, which can greatly improve the device performance of the ultraviolet photodetector diode.
  • a method for preparing an ultraviolet photodetector based on a Ga 2 O 3 material includes:
  • a bottom electrode is formed on a lower surface of the substrate.
  • the embodiment of the invention proposes another preparation method of a Ga 2 O 3 /GaN/SiC photodetector diode based on double heterojunction.
  • the method includes:
  • a second metal material is deposited on the entire surface of the substrate to form a top electrode to ultimately form the photodetector diode.
  • the invention relates to a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 and a manufacturing method thereof.
  • the method includes:
  • a bottom electrode is formed on the lower surface of the ⁇ -Ga 2 O 3 substrate to finally form an APD detector diode.
  • the photodetector of the embodiment of the invention adopts a Ga 2 O 3 material, and the light transmittance in the sun blind zone can reach 80% or more, even to 90%, and is suitable for the light absorbing layer, and the electrical properties of the transparent conductive material are also It is beneficial to improve the light absorbing ability of the light absorbing layer, thereby greatly improving the device performance of the photodetecting diode.
  • FIG. 1 is a schematic diagram of a method for preparing an ultraviolet photodetector based on a Ga 2 O 3 material according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of a Ga 2 O 3 /GaN/SiC photodetector diode based on a double heterojunction according to an embodiment of the present invention
  • FIG. 3 is a top plan view of a double heterojunction-based Ga 2 O 3 /GaN/SiC photodetector diode according to an embodiment of the present invention
  • FIG. 4 is a schematic flow chart of a method for preparing a Ga 2 O 3 /GaN/SiC photodetector diode based on double heterojunction according to an embodiment of the present invention
  • 5a-5g are schematic diagrams showing a method for fabricating a Ga 2 O 3 /GaN/SiC photodetector diode based on a double heterojunction according to an embodiment of the present invention
  • 6a is a schematic structural diagram of a first lithography mask according to an embodiment of the present invention.
  • 6b is a schematic structural diagram of a second lithography mask according to an embodiment of the present invention.
  • FIG. 7 is a schematic cross-sectional view of a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • FIG. 8 is a schematic top view of a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • FIG. 9 is a schematic flow chart of a method for fabricating a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • 10a-10g are schematic diagrams showing a method for fabricating a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • FIG. 11a is a schematic diagram of a third lithography mask according to an embodiment of the present invention.
  • FIG. 11b is a schematic diagram of a fourth lithography mask according to an embodiment of the present invention.
  • FIG. 11c is a schematic diagram of a fifth lithography mask according to an embodiment of the present invention.
  • FIG. 1 is a schematic diagram of a method for preparing an ultraviolet photodetector based on a Ga 2 O 3 material according to an embodiment of the present invention.
  • the method can include:
  • Step 101 selecting a substrate
  • Step 102 forming a Ga 2 O 3 layer on the upper surface of the substrate
  • Step 103 forming a top electrode on the Ga 2 O 3 layer
  • Step 104 forming a bottom electrode on the lower surface of the substrate.
  • the Ga 2 O 3 material is used, and the light transmittance in the sun blind zone can be more than 80%, or even 90%, which is suitable for the light absorbing layer, and the electrical properties of the transparent conductive layer are also favorable for improving the light absorbing layer.
  • the light absorption capability further increases the device performance of the photodetector diode.
  • the ultraviolet photodetector based on Ga 2 O 3 material may include two structures: deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 and Ga 2 O 3 /GaN/SiC based on double heterojunction. Photodetector diode. The following focuses on the detailed description of the two types of UV photodetectors.
  • FIG. 2 is a schematic cross-sectional view of a double heterojunction-based Ga 2 O 3 /GaN/SiC photodetecting diode according to an embodiment of the present invention
  • FIG. 3 is a schematic diagram of an embodiment of the present invention.
  • the ultraviolet photodetection diode of the present embodiment includes a SiC substrate 201, an N-type homoepitaxial layer 202, a GaN layer 203, an N-type Ga 2 O 3 layer 204, a bottom electrode 205, a top electrode 206, and a light absorbing layer 207.
  • the SiC substrate 201 is an N-type 4H-SiC or 6H-SiC material;
  • the N-type homoepitaxial layer 202 is an N-doped SiC having a doping concentration of 10 15 cm -3 ;
  • the GaN layer 203 is doped a hetero-N element P-type GaN material having a doping concentration of 10 17 cm -3 ;
  • the N-type Ga 2 O 3 layer 204 is doped with Sn, Si, Al, ⁇ -Ga 2 O 3 (-201), ⁇ - The Ga 2 O 3 (010) or ⁇ -Ga 2 O 3 (001) material has a doping concentration of the order of 10 17 cm -3 ;
  • the light absorbing layer 207 is a material of Ti, Al, Ni or the like.
  • the top electrode 206 may be a metal material such as Au, Al, Ti, Sn, Ge, In, Ni, Co, Pt, W, Mo, Cr, Cu, Pb, or a mixture of two or more of these metals or ITO.
  • a conductive compound is formed. Further, it may have a two-layer structure composed of two or more different metals, for example, Al/Ti.
  • the bottom electrode 205 may be a metal material such as Au, Al, Ti, Sn, Ge, In, Ni, Co, Pt, W, Mo, Cr, Cu, Pb, or a conductive compound including two or more of these metals or ITO. form. Further, it is possible to have a two-layer structure composed of two or more different metals, for example, an Al/Ti laminated bimetal material.
  • the wide bandgap semiconductor material Ga 2 O 3 is suitable for photodetection of deep ultraviolet light daylight blind zone due to the light transmittance of the material in the solar blind zone of 80% or more, and its photoelectric sensitivity is high. Both sapphire transparency and SiC conductivity are ideal materials for photodetector diode research.
  • FIG. 4 is a schematic flow chart of a method for fabricating a Ga 2 O 3 /GaN/SiC photodetector diode based on a double heterojunction according to an embodiment of the present invention. The method comprises the following steps:
  • Step 401 selecting a SiC substrate
  • Step 402 continuously growing a homoepitaxial layer, a GaN layer, and a Ga 2 O 3 layer on the surface of the SiC substrate;
  • Step 403 forming a light absorbing layer on the surface of the Ga 2 O 3 layer;
  • Step 404 depositing a first metal material on the lower surface of the entire substrate to form a bottom electrode
  • Step 405 depositing a second metal material on the entire surface of the substrate to form a top electrode to finally form a photodetection diode.
  • step 401 can include:
  • Step 4011 selecting an N-type 4H-SiC or 6H-SiC material as the SiC substrate;
  • Step 4012 cleaning the SiC substrate by using a RCA standard cleaning process.
  • Step 402 can include:
  • Step 4021 using an LPCVD process, growing an N-doped SiC material on the surface of the SiC substrate to form an N-type homoepitaxial layer;
  • Step 4022 using an MOCVD process, growing a N-doped GaN material on the homoepitaxial surface to form a GaN layer;
  • Step 4023 Using a MBE process, a Ga 2 O 3 layer is formed by growing a ⁇ -Ga 2 O 3 material having a doping element of an element such as Sn, Si, or Al on the surface of the GaN layer.
  • Step 403 can include:
  • a third metal material is sputtered on the surface of the Ga 2 O 3 layer by a magnetron sputtering process to form a light absorbing layer.
  • the Ni material is used as a target, and argon gas is used as a sputtering gas to pass into the sputtering cavity, and the working power is 100 W and the vacuum degree is 6 ⁇ 10 ⁇ 4 to 1.3 ⁇ 10 ⁇ 3 Pa.
  • a Ni material was sputtered on the surface of the Ga 2 O 3 layer as a third metal material.
  • Step 404 can include:
  • Step 4041 sputtering a first metal material on a lower surface of the entire substrate including a SiC substrate, a homoepitaxial layer, a GaN layer, a Ga 2 O 3 layer, and a light absorbing layer by a magnetron sputtering process;
  • Step 4042 Under the atmosphere of nitrogen and argon, an ohmic contact is formed at a lower surface of the entire substrate with the surface of the first metal material by a rapid thermal annealing process to complete the preparation of the bottom electrode.
  • the step 4041 may include: using a Ni material as a target, and using argon as a sputtering gas to pass into the sputtering cavity, the working power is 100 W, and the degree of vacuum is 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 . Under the condition of Pa, a Ni material was sputtered on the lower surface of the entire substrate as the first metal material.
  • Step 405 can include:
  • Step 4051 using a second mask to grow a second metal on the entire surface of the substrate including the SiC substrate, the homoepitaxial layer, the GaN layer, the Ga 2 O 3 layer, and the light absorbing layer by a magnetron sputtering process material;
  • Step 4052 An ohmic contact is formed at an upper surface of the entire substrate and a surface of the second metal material by a rapid thermal annealing process under an atmosphere of nitrogen and argon to complete the preparation of the top electrode.
  • the photodetecting diode of the embodiment adopts a double heterojunction structure, thereby forming a double barrier, which can effectively reduce leakage current, thereby greatly improving the device reliability of the photodiode, and the utility model has high practicability, and is currently in the SiC lining.
  • the process of homoepitaxial growth and growth of GaN layers on the bottom has been mature, and a mature process of growing Ga 2 O 3 on a GaN substrate has also appeared.
  • the present invention combines the two processes and has high practical value.
  • the photodetecting diode of the present invention applies a Ga 2 O 3 material to the light absorbing layer, and fully exerts its excellent performance in ultraviolet light detection, and the light transmittance of the material in the sun blind area can reach 80% or even 90%. It is very suitable for application to the light absorbing layer.
  • its transparent conductive electrical properties are also beneficial to improve the light absorbing ability of the light absorbing layer, thereby greatly improving the device performance of the photodetecting diode.
  • FIG. 5a - FIG. 5g and FIG. 6a and FIG. 6b are a preparation method of a double heterojunction-based Ga 2 O 3 /GaN/SiC photodetector diode according to an embodiment of the present invention.
  • FIG. 6 is a schematic structural diagram of a first mask according to an embodiment of the present invention
  • FIG. 6b is a schematic structural diagram of a second mask according to an embodiment of the present invention.
  • This embodiment describes the preparation method of the double heterojunction-based Ga 2 O 3 /GaN/SiC photodetecting diode of the present invention in detail based on the above embodiments.
  • Step 501 Referring to FIG. 5a, the SiC substrate 501 is prepared to have a thickness of 350 ⁇ m, and the substrate is subjected to RCA standard cleaning;
  • Step 502 Referring to FIG. 5b, an N-type homoepitaxial layer 502 is formed by LPCVD on the SiC substrate 501 prepared in step 501, the doping concentration is on the order of 10 15 cm -3 , the doping element is N, and the thickness is 5 ⁇ 10um;
  • Step 503 Referring to FIG. 5c, a GaN layer 503 is formed by MOCVD on the N-type homoepitaxial layer 502 prepared in step 502, the doping concentration is on the order of 10 17 cm -3 , the doping element is N, and the thickness is 5 ⁇ 10um;
  • Step 504 Referring to FIG. 5d, the ⁇ -Ga 2 O 3 layer 504 is grown by the Molecular Beam Epitaxy (MBE) process on the GaN layer 503 prepared in step 503, and the doping concentration is 10 17 cm -3 .
  • MBE Molecular Beam Epitaxy
  • Magnesium, doping elements are Sn, Si, Al and other elements, the thickness is 5 ⁇ 10um;
  • Step 505 Please refer to FIG. 5e and FIG. 6a, the ⁇ -Ga 2 O 3 layer 504 prepared in step 504 is formed into a Ni light absorbing layer 507 by magnetron sputtering using a first mask;
  • the sputtering target is made of nickel with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • the collector Ni was prepared under the conditions of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa, an argon flow rate of 20 to 30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 100 W. It is 30 nm to 100 nm.
  • Step 506 Referring to FIG. 5f, the Ni bottom electrode 505 is grown by magnetron sputtering on the lower surface of the N-type SiC substrate 501 prepared in Step 501.
  • the sputtering target is made of nickel with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • Step 507 Referring to FIG. 5g and FIG. 6b, the Ni/Au top electrode 506 is grown by magnetron sputtering using a second mask on the light absorbing layer 507 and the Ga 2 O 3 layer 504 prepared in step 505.
  • the sputtering target is made of nickel with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • the top electrode nickel is prepared under the conditions of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa, an argon flow rate of 20-30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 20 W to 100 W.
  • the electrode thickness is 20 nm to 30 nm.
  • the sputtering target is made of Au with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • the gate electrode gold is prepared under the conditions of a vacuum of 6 ⁇ 10 -4 -1.3 ⁇ 10 -3 Pa, an argon flow rate of 20-30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 20 W-100 W.
  • the electrode thickness is 150nm-200nm, then 500 under nitrogen or argon The fire formed for 3 min to form an ohmic contact.
  • the photodetecting diode of the invention adopts a double heterojunction structure, thereby forming a double barrier, which can effectively reduce leakage current, thereby greatly improving the device reliability of the photodiode, and the utility model has high practicability, and is currently in the SiC substrate.
  • the process of homoepitaxial growth and growth of a GaN layer has matured, and a mature process of growing Ga 2 O 3 on a GaN substrate has also appeared.
  • the present invention combines the two processes and has high practical value.
  • the photodetecting diode of the present invention applies a Ga 2 O 3 material to the light absorbing layer, and fully exerts its excellent performance in ultraviolet light detection, and the light transmittance of the material in the sun blind area can reach 80% or even 90%. It is very suitable for application to the light absorbing layer.
  • its transparent conductive electrical properties are also beneficial to improve the light absorbing ability of the light absorbing layer, thereby greatly improving the device performance of the photodetecting diode.
  • Ga 2 O 3 a wide bandgap semiconductor material, is highly suitable for photodetection of deep ultraviolet light in the solar blind zone due to its light transmittance in the solar blind zone of 80% or more. It has high photoelectric sensitivity and transparency of sapphire.
  • the electrical conductivity of SiC and SiC is an ideal semiconductor material for the research of optoelectronic devices, especially deep ultraviolet photodetectors.
  • FIG. 7 is a schematic cross-sectional view of a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • FIG. 8 is a schematic diagram of an embodiment of the present invention.
  • the APD detecting diode includes a ⁇ -Ga 2 O 3 substrate 701, an N-type homoepitaxial layer 702, a P-layer heteroepitaxial layer 703, a top electrode 704, and a bottom electrode 705.
  • the ⁇ -Ga 2 O 3 substrate 701 is ⁇ -Ga 2 O 3 (-201), ⁇ -Ga 2 O 3 (010) or ⁇ -Ga 2 O 3 which are undoped or doped with Sn, Si, Al ( 001) material;
  • the N-type homoepitaxial layer 702 is a ⁇ -Ga 2 O 3 layer doped with Sn, Si, Al, the doping concentration is on the order of 10 15 cm -3 ;
  • the P-type hetero epitaxial layer 703 is Ir 2 O 3 layer, doping concentration is on the order of 10 19 -10 20 cm -3 ;
  • top electrode 704 and bottom electrode 705 are Au, Al, Ti, Sn, Ge, In, Ni, Co, Pt, W, Mo, Cr
  • a metal material such as Cu or Pb is formed of a conductive compound such as two or more of these metals or ITO. Further, it may have a two-layer structure composed of two or more different metals, such as Al/Ti or Ti/A
  • FIG. 9 is a schematic flow chart of a method for fabricating a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention. The method comprises the following steps:
  • Step 901 selecting a ⁇ -Ga 2 O 3 substrate
  • Step 902 growing a ⁇ -Ga 2 O 3 material on the surface of the ⁇ -Ga 2 O 3 substrate to form a homoepitaxial layer;
  • Step 903 respectively growing Ir 2 O 3 material on the surface growth of the homoepitaxial layer to form a heteroepitaxial layer
  • Step 904 etching the heteroepitaxial layer and the homoepitaxial layer to form a ladder structure
  • Step 905 forming a top electrode on the surface of the heteroepitaxial layer
  • Step 906 forming a bottom electrode on the lower surface of the ⁇ -Ga 2 O 3 substrate to finally form an APD detector diode.
  • step 902 it may include:
  • An N-type ⁇ -Ga 2 O 3 material having a doping concentration of 1 ⁇ 10 15 to 1 ⁇ 10 16 cm ⁇ 3 is grown on the surface of the ⁇ -Ga 2 O 3 substrate by a molecular beam epitaxy process to form a homoepitaxial layer; Wherein, the thickness of the homoepitaxial layer is adjusted according to the avalanche gain coefficient.
  • step 903 it may include:
  • a P-type Ir 2 O 3 material having a doping concentration of 1 ⁇ 10 19 to 1 ⁇ 10 20 cm -3 is grown on the surface of the homoepitaxial layer by a CVD process to form a heteroepitaxial layer.
  • step 904 it may include:
  • Step 9041 using a third photolithography mask, etching the hetero epitaxial layer by a tilt etching process to form a first trapezoidal structure in the heteroepitaxial layer;
  • Step 9042 using a fourth photolithography mask, etching the homoepitaxial layer by a selective tilt etching process to form a second trapezoidal structure in the homoepitaxial layer to form a trapezoidal structure.
  • step 905 it may include:
  • a fifth photolithographic mask is used to sputter the first composite metal material on the surface of the heteroepitaxial layer by a magnetron sputtering process to form a top electrode.
  • the first composite metal material is sputtered on the surface of the heteroepitaxial layer by a magnetron sputtering process, including:
  • the Ti material is used as a sputtering target, and Ar gas is used as a sputtering gas to pass into the sputtering chamber. Under the condition of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa and an operating frequency of 100 W, the difference is different.
  • the surface of the epitaxial layer is sputtered to form a Ti layer;
  • the Au material is used as a sputtering target, and Ar gas is used as a sputtering gas to pass into the sputtering chamber. Under a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa and an operating frequency of 100 W, Ti is used. The layer surface is sputtered to form an Au layer to form a first composite metal material.
  • step 906 it may include:
  • a second composite metal material is sputtered on the lower surface of the ⁇ -Ga 2 O 3 substrate by a magnetron sputtering process to form a bottom electrode.
  • the second composite metal material is sputtered on the lower surface of the ⁇ -Ga 2 O 3 substrate by a magnetron sputtering process, including:
  • the Ti material was used as a sputtering target, and Ar gas was used as a sputtering gas to pass into the sputtering chamber.
  • the vacuum was 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa and the operating frequency was 100 W.
  • a lower surface of the -Ga 2 O 3 substrate is sputtered to form a Ti layer;
  • the Au material is used as a sputtering target, and Ar gas is used as a sputtering gas to pass into the sputtering chamber. Under a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa and an operating frequency of 100 W, Ti is used. The layer surface is sputtered to form an Au layer to form a second composite metal material.
  • step 902 the method further includes:
  • Step x1 immersing the ⁇ -Ga 2 O 3 substrate in methanol, acetone and methanol, respectively, and then washing with deionized water and flowing deionized water to complete organic cleaning;
  • Step x2 The ⁇ -Ga 2 O 3 substrate is immersed in deionized water, soaked in SPM solution or Piranha solution, then immersed in deionized water and heated, and the acid treatment is completed by cooling treatment.
  • the invention firstly proposes a preparation method of a novel ultraviolet APD detector based on Ga 2 O 3 material.
  • the invention adopts a Ga 2 O 3 material to fully exert the extremely high light transmittance and transparency of the material in the deep ultraviolet light region and the visible light region, and the material far exceeds the high band gap width of materials such as SiC and GaN to ensure the APD.
  • the detector has a high withstand voltage and a high breakdown electric field, so that the novel ultraviolet APD detector of the present invention is more suitable for extreme environments such as high frequency, high radiation and high voltage than the previous APD detector, and the material is excellent in thermal stability. Sexual and chemical stability In the high temperature extreme environment, the device reliability is improved compared with the previous APD detector, and its detection performance will be better than the previous APD detector.
  • the avalanche gain coefficient M can be adjusted by adjusting the thickness of the N/P-type conductive Ga 2 O 3 layer in the structure, and selecting a suitable M makes the signal-to-noise ratio of the invention good, has a low excess noise, and optimizes the device. Photodetection sensitivity.
  • FIG. 10 is a schematic diagram of a method for fabricating a deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 according to an embodiment of the present invention
  • FIG. 11a is a first photolithography method according to an embodiment of the present invention
  • FIG. 11b is a schematic diagram of a second lithography mask according to an embodiment of the present invention
  • FIG. 11c is a schematic diagram of a third lithography mask according to an embodiment of the present invention.
  • the method for fabricating the deep ultraviolet APD detecting diode based on Ir 2 O 3 /Ga 2 O 3 of the present invention is described in detail as follows:
  • Step 1001 Referring to FIG. 10a, a substrate ⁇ -Ga 2 O 3 1001 is prepared, and the thickness is 200 ⁇ m-600 ⁇ m, and the substrate is subjected to pretreatment cleaning.
  • the substrate is selected from ⁇ -Ga 2 O 3 1001.
  • Reason It belongs to a new generation of ultra-wide band gap semiconductor materials with a band gap of 4.7 to 4.9 eV and a theoretical breakdown field strength of 8 MV/cm, which is superior to SiC and GaN.
  • the wide bandgap material in addition to its single crystal substrate material, can be obtained by a solution method, and the preparation cost is low.
  • the material itself is transparent and has a high light transmittance. Therefore, the APD detector prepared by ⁇ -Ga 2 O 3 is more sensitive to deep ultraviolet (wavelength range 200nm to 280nm) detection and the working bias voltage is not high. .
  • the substrate is firstly organically cleaned, the first step of methanol soaking for 3 minutes, the second step of acetone soaking for 3 minutes, the third step of methanol soaking for 3 minutes, the fourth step of deionized water for 3 minutes, and the fifth step of flowing deionized water for 5 minutes;
  • the substrate can be replaced by a thermal etching of 1 ⁇ m of SiO 2 on a 200 ⁇ m-600 ⁇ m silicon substrate.
  • the above cleaning steps are not required, and the RCA standard cleaning is used. After the replacement, the insulation effect is deteriorated, and the manufacturing process is more complicated.
  • Step 1002 Referring to FIG. 10b, the N-type doped ⁇ -Ga 2 O 3 material is grown by molecular beam epitaxy on the ⁇ -Ga 2 O 3 substrate 1001 prepared in step 1001 to form a homoepitaxial layer 1002, doped.
  • the elements may be Sn, Si, Al, doped at a concentration of 10 15 cm -3 , and have a thickness of 5-10 um.
  • Step 1003 Referring to FIG. 10c, a P-type doped region Ir 2 O 3 is grown by a CVD process on the N-type homoepitaxial layer 1002 prepared in Step 1002 to form a heteroepitaxial layer 1003 having a doping concentration of 10 19 to 10 20 . It is of the order of cm -3 and has a thickness of 5-10um.
  • Step 1004 Referring to FIG. 10d and FIG. 11a, a third photolithographic mask is used on the entire substrate surface formed in step 1003 and a trapezoidal structure is formed in the P-type hetero epitaxial layer 1003 by a tilt etching process;
  • Step 1005 Referring to FIG. 10e and FIG. 11b, the entire substrate surface formed in step 1004 is formed into a trapezoidal structure in the N-type homoepitaxial layer 1002 by a selective tilt etching process using a fourth photolithography mask;
  • the oblique etching process is a tilting mesa etching process, and the specific process is as follows: first, ICP dry etching is performed for 5 seconds by using a BCl 3 -based etching gas, followed by immersion in a 5% HF solution for 10 s; Cycle until the material being etched is completely etched.
  • Step 1006 Referring to FIG. 10f and FIG. 11b, the fifth photolithographic mask is prepared on the P-type hetero epitaxial layer 1003 prepared in step 1005, and the top electrode Ti/Au is grown by magnetron sputtering;
  • the sputter target is made of Ti with a mass ratio of >99.99%, and Ar with a mass percent purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the magnetron sputtering is performed with high purity argon gas.
  • the equipment chamber was cleaned for 5 minutes and then evacuated.
  • the top electrode Ti was prepared under the conditions of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa, an argon flow rate of 20 to 30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 100 W. It is 20 nm to 30 nm.
  • the sputtering target is made of Au with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • the top electrode gold is prepared under the conditions of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa, an argon flow rate of 20 to 30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 20 W to 100 W.
  • the electrode thickness is 200nm ⁇ 300nm, then 500 under nitrogen or argon The fire formed for 3 min to form an ohmic contact.
  • Step 1007 Please refer to FIG. 10g, the bottom electrode Ti/Au is grown by magnetron sputtering on the lower surface of the substrate;
  • the sputtering target is made of Ti having a mass ratio of >99.99%, and Ar having a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the magnetron sputtering is performed with high purity argon gas.
  • the equipment chamber was cleaned for 5 minutes and then evacuated.
  • the gate electrode Ti was prepared under the conditions of a vacuum of 6 ⁇ 10 ⁇ 4 ⁇ 1.3 ⁇ 10 ⁇ 3 Pa, an argon flow rate of 20-30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 100 W. It is 20 nm to 30 nm.
  • the sputtering target is made of Au with a mass ratio of >99.99%, and Ar with a mass percentage of purity of 99.999% is used as a sputtering gas to pass into the sputtering chamber.
  • the chamber of the magnetron sputtering device is treated with high purity argon gas. Wash for 5 minutes and then evacuate.
  • the gate electrode gold is prepared under the conditions of a vacuum of 6 ⁇ 10 -4 to 1.3 ⁇ 10 -3 Pa, an argon flow rate of 20 to 30 cm 3 /sec, a target base distance of 10 cm, and an operating power of 20 W to 100 W.
  • the electrode thickness is 200nm ⁇ 300nm, then 500 under nitrogen or argon The fire formed for 3 min to form an ohmic contact.
  • the ultraviolet APD detector of the present invention firstly uses an optically superior Ga 2 O 3 material to give full play to the extremely high light transmittance and transparency of the material in the deep ultraviolet region and the visible region, and the light transmittance of the material in the deep ultraviolet region.
  • the electrical properties of the material ensure that the novel ultraviolet APD detector of the present invention has a high withstand voltage and a high breakdown electric field, which is far superior to the high band gap of materials such as SiC and GaN.
  • the new UV APD detector is more suitable for extreme environments such as high frequency, high radiation, high temperature and high pressure. In extreme environments, not only the device reliability is greatly improved, but also the detection performance is better than the current APD detector.
  • the device structure of the novel ultraviolet APD detector of the present invention is improved on the basis of a conventional APD detector, that is, an avalanche photodiode, which can effectively increase the body avalanche breakdown voltage and thereby increase the avalanche gain coefficient M, and at the same time adjust the structure.
  • the thickness of the N/P-type conductive Ga 2 O 3 layer can be adjusted by M. Selecting a suitable M makes the signal-to-noise ratio of the invention good, and has a low excess noise, so that the device achieves optimal photodetection sensitivity.
  • Example Ga 2 O 3 by using a material structure in the photodetector, the full material of high light transmission and transparency in the deep ultraviolet region and the visible region, can significantly improve the performance of the photovoltaic device of the present invention detecting diode.

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Abstract

一种基于Ga 2O 3材料的紫外光电探测器的制备方法。其中该制备包括:选取衬底(步骤101);在衬底上形成Ga 2O 3层(步骤102);在Ga 2O 3层上形成顶电极(步骤103);在该衬底下表面形成底电极(步骤104)。采用Ga 2O 3材料,在日盲区光透率可达80%以上,甚至到90%,适合应用于光吸收层,此外其透明导电的电学特性也有利于提高光吸收层的光吸收能力,进而大幅提高光电探测二极管的器件性能。

Description

基于Ga2O3材料的紫外光电探测器的制备方法 技术领域
本发明属于集成电路技术领域,特别涉及一种基于Ga2O3材料的紫外光电探测器的制备方法。
背景技术
随着近年来天文、高能物理、空间技术等领域的研究与探索工作的不断深入,及其在宇宙探测、人造卫星等方面应用前景的迅速拓展,对于光线尤其紫外光的探测器的要求越来越高,如光电对抗中紫外对抗与反对抗技术就愈发受到军方的关注。通常波长在10~400nm的电磁波成为紫外线,既不同于可见光辐射,又不同于红外辐射;其中来自太阳辐射的紫外线中被大气层几乎完全吸收的谱区被称为日盲区,是紫外探测中较难探测到的区域。
雪崩光电二极管(Avalanche Photo Diode,简称APD)探测器与光电探测二极管都是一种PN结型的光电检测二极管,利用了载流子的雪崩倍增效应来放大光信号以提高检测灵敏度,一般可测量紫外到红外光区域,在军事高技术与民品市场的开发中具有很大的使用价值,如在日盲区对尾烟或羽烟中能释放大量紫外辐射的飞行目标进行实时探测或有效跟踪。
对于目前的APD探测器由于不具备极高的耐压性和抗击穿性,因此并不适合高频、高辐射、高温高压等极端环境下的应用。另外,光电检测二极管仍然存在光吸收能力弱,且在紫外光探测方面能力不强等问题。
发明内容
因此,本发明提出一种基于Ga2O3材料的紫外光电探测器的制备方法,其可实现大幅提高紫外光电探测二极管的器件性能。
具体地,本发明实施例提出的一种基于Ga2O3材料的紫外光电探测器的制备方法,包括:
选取衬底;
在所述衬底上表面形成Ga2O3层;
在所述Ga2O3层上形成顶电极;
在所述衬底下表面形成底电极。
本发明实施例提出了另一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的制备方法。该方法包括:
选取SiC衬底;
在SiC衬底表面连续生长同质外延层、GaN层及Ga2O3层;在Ga2O3层表面形成光吸收层;
在整个衬底下表面淀积第一金属材料形成底电极;
在整个衬底上表面淀积第二金属材料形成顶电极以最终形成所述光电探测二极管。
本发明涉及一种基于Ir2O3/Ga2O3的深紫外APD探测二极管及其制作方法。该方法包括:
选取β-Ga2O3衬底;
在β-Ga2O3衬底上表面生长β-Ga2O3材料形成同质外延层;
在同质外延层表面生长上生长Ir2O3材料形成异质外延层;
刻蚀异质外延层和同质外延层形成梯形结构;
在异质外延层表面形成顶电极;
在β-Ga2O3衬底下表面形成底电极,最终形成APD探测器二极管。
本发明实施例的光电探测器,通过采用Ga2O3材料,在日盲区光透率可达80%以上,甚至到90%,适合应用于光吸收层,此外其透明导电的电学特性也有利于提高光吸收层的光吸收能力,进而大幅提高光电探测二极管的器 件性能。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下特举较佳实施例,并配合附图,详细说明如下。
附图概述
图1为本发明实施例提供的一种基于Ga2O3材料的紫外光电探测器的制备方法示意图。
图2为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的截面示意图;
图3为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的俯视示意图;
图4为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的制备方法流程示意图;
图5a-图5g为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的制备方法示意图;
图6a为本发明实施例提供的一种第一光刻掩膜版的结构示意图;
图6b为本发明实施例提供的一种第二光刻掩膜版的结构示意图;
图7为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的截面示意图;
图8为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的俯视示意图;
图9为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的制作方法流程示意图;
图10a-图10g为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的制作方法示意图;
图11a为本发明实施例提供的一种第三光刻掩膜版的示意图;
图11b为本发明实施例提供的一种第四光刻掩膜版的示意图;以及
图11c为本发明实施例提供的一种第五光刻掩膜版的示意图。
本发明的较佳实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例,对依据本发明提出的基于Ga2O3材料的紫外光电探测器的制备方法其具体实施方式、方法、步骤及功效,详细说明如后。
有关本发明的前述及其他技术内容、特点及功效,在以下配合参考图式的较佳实施例详细说明中将可清楚的呈现。通过具体实施方式的说明,当可对本发明为达成预定目的所采取的技术手段及功效得以更加深入且具体的了解,然而所附图式仅是提供参考与说明之用,并非用来对本发明加以限制。
请参见图1,图1为本发明实施例提供的一种基于Ga2O3材料的紫外光电探测器的制备方法示意图。该方法可以包括:
步骤101、选取衬底;
步骤102、在衬底上表面形成Ga2O3层;
步骤103、在Ga2O3层上形成顶电极;
步骤104、在衬底下表面形成底电极。
本发明实施例,采用Ga2O3材料,在日盲区光透率可达80%以上,甚至到90%,适合应用于光吸收层,此外其透明导电的电学特性也有利于提高光吸收层的光吸收能力,进而大幅提高光电探测二极管的器件性能。
该基于Ga2O3材料的紫外光电探测器,可以包括两种结构:基于Ir2O3/Ga2O3的深紫外APD探测二极管和基于双异质结的Ga2O3/GaN/SiC 光电探测二极管。以下重点对两种结构的紫外光电探测器进行详细描述。
【实施例一】
请参见图2及图3,图2为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的截面示意图,图3为本发明实施例提供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的俯视示意图。本实施的紫外光电探测二极管包括:SiC衬底201、N型同质外延层202、GaN层203、N型Ga2O3层204、底电极205、顶电极206、光吸收层207。
其中,SiC衬底201为N型的4H-SiC或6H-SiC材料;N型同质外延层202为掺杂N元素的SiC,掺杂浓度1015cm-3量级;GaN层203为掺杂N元素的P型GaN材料,掺杂浓度1017cm-3量级;N型Ga2O3层204为掺杂Sn、Si、Al的β-Ga2O3(-201)、β-Ga2O3(010)或β-Ga2O3(001)材料,掺杂浓度1017cm-3量级;光吸收层207为Ti、Al、Ni等材料。
进一步地,顶电极206可以为Au、Al、Ti、Sn、Ge、In、Ni、Co、Pt、W、Mo、Cr、Cu、Pb等金属材料、包含这些金属中2种以上合金或ITO等导电性化合物形成。另外,可以具有由不同的2种以上金属构成的2层结构,例如Al/Ti。底电极205可以为Au、Al、Ti、Sn、Ge、In、Ni、Co、Pt、W、Mo、Cr、Cu、Pb等金属材料、包含这些金属中2种以上合金或ITO等导电性化合物形成。另外,可以具有由不同的2种及以上金属构成的2层结构,例如Al/Ti叠层双金属材料。
需要说明的是:宽禁带半导体材料Ga2O3,因材料在日盲区的光透率可达80%甚至90%以上而极适合于深紫外光日盲区的光电探测,其光电灵敏度高,兼具蓝宝石的透明性与SiC的导电性,是进行光电探测二极管研究的理想材料。
请参见图4,图4为本发明实施例提供的一种基于双异质结的 Ga2O3/GaN/SiC光电探测二极管的制备方法流程示意图。该方法包括如下步骤:
步骤401、选取SiC衬底;
步骤402、在SiC衬底表面连续生长同质外延层、GaN层及Ga2O3层;
步骤403、在Ga2O3层表面形成光吸收层;
步骤404、在整个衬底下表面淀积第一金属材料形成底电极;
步骤405、在整个衬底上表面淀积第二金属材料形成顶电极以最终形成光电探测二极管。
其中,步骤401可以包括:
步骤4011、选取N型的4H-SiC或6H-SiC材料作为SiC衬底;
步骤4012、利用RCA标准清洗工艺对SiC衬底进行清洗。
步骤402可以包括:
步骤4021、利用LPCVD工艺,在SiC衬底表面生长掺杂N元素的SiC材料以形成N型的同质外延层;
步骤4022、采用MOCVD工艺,在同质外延表面生长掺杂N元素的GaN材料以形成GaN层;
步骤4023、利用MBE工艺,在GaN层表面生长掺杂元素为Sn、Si、Al等元素的β-Ga2O3材料形成Ga2O3层。
步骤403可以包括:
采用第一掩膜板,利用磁控溅射工艺在Ga2O3层表面溅射第三金属材料形成光吸收层。具体地,以Ni材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为100W,真空度为6×10-4~1.3×10-3Pa的条件下,在Ga2O3层表面溅射Ni材料以作为第三金属材料。
步骤404可以包括:
步骤4041、利用磁控溅射工艺在包括SiC衬底、同质外延层、GaN层、 Ga2O3层及光吸收层的整个衬底的下表面溅射第一金属材料;
步骤4042、在氮气和氩气的气氛下,利用快速热退火工艺在整个衬底的下表面与第一金属材料表面处形成欧姆接触以完成底电极的制备。
进一步地,步骤4041可以包括:以Ni材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为100W,真空度为6×10-4~1.3×10-3Pa的条件下,在整个衬底的下表面溅射Ni材料以作为第一金属材料。
步骤405可以包括:
步骤4051、采用第二掩膜板,利用磁控溅射工艺在在包括SiC衬底、同质外延层、GaN层、Ga2O3层及光吸收层的整个衬底上表面生长第二金属材料;
步骤4052、在氮气和氩气的气氛下,利用快速热退火工艺在整个衬底的上表面与第二金属材料表面处形成欧姆接触以完成顶电极的制备。
需要重点强调的是,步骤404和步骤405中的底电极和顶电极的工艺流程并不固定。可以先进行底电极的制备,也可以先进行顶电极的制备,此处不做任何限制。
本实施例的光电探测二极管采用了双异质结结构,从而形成双势垒,可有效降低漏电流,从而大幅提高光电二极管的器件可靠性,且本发明的实用性较高,目前在SiC衬底上进行同质外延和生长GaN层的工艺已成熟,也出现过在GaN衬底上生长Ga2O3的成熟工艺,本发明将两工艺结合,实用价值高。
另外,本发明的光电探测二极管将Ga2O3材料应用于光吸收层,充分发挥其在紫外光探测方面的卓越性能,该材料在日盲区光透率可达80%以上,甚至到90%,十分适合应用于光吸收层,此外其透明导电的电学特性也有利于提高光吸收层的光吸收能力,进而大幅提高光电探测二极管的器件性能。
请一并参见图5a-图5g及图6a和图6b,图5a-图5h为本发明实施例提 供的一种基于双异质结的Ga2O3/GaN/SiC光电探测二极管的制备方法示意图,图6a为本发明实施例提供的一种第一掩膜版的结构示意图,图6b为本发明实施例提供的一种第二掩膜版的结构示意图。本实施例在上述实施例的基础上,对本发明的基于双异质结的Ga2O3/GaN/SiC光电探测二极管的制备方法进行详细说明如下:
步骤501:请参见图5a,准备SiC衬底501,厚度为350μm,对衬底进行RCA标准清洗;
步骤502:请参见图5b,在步骤501所准备的SiC衬底501上通过LPCVD生成N型同质外延层502,掺杂浓度在1015cm-3量级,掺杂元素为N,厚度在5~10um;
步骤503:请参见图5c,在步骤502所准备的N型同质外延层502上通过MOCVD形成GaN层503,掺杂浓度在1017cm-3量级,掺杂元素为N,厚度在5~10um;
步骤504:请参见图5d,在步骤503所准备的GaN层503上通过分子束外延(Molecular Beam Epitaxy,简称MBE)工艺生长β-Ga2O3层504,掺杂浓度在1017cm-3量级,掺杂元素为Sn、Si、Al等元素,厚度在5~10um;
步骤505:请参见图5e及图6a,在步骤504所准备的β-Ga2O3层504使用第一掩膜版,通过磁控溅射形成Ni光吸收层507;
溅射靶材选用质量比纯度>99.99%的镍,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20~30cm3/秒、靶材基距为10cm和工作功率为100W的条件下,制备集电极Ni,电极厚度为30nm~100nm。
步骤506:请参见图5f,在步骤501所准备的N型SiC衬底501下表面通过磁控溅射生长Ni底电极505。
溅射靶材选用质量比纯度>99.99%的镍,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20~30cm3/秒、靶材基距为10cm和工作功率为100W的条件下,制备集电极Ni,电极厚度为150nm~250nm,之后在1000
Figure PCTCN2017114675-appb-000001
氮气或氩气环境下快速热退火3min。
步骤507:请参见图5g及图6b,在步骤505所准备的光吸收层507和Ga2O3层504上使用第二掩膜版,通过磁控溅射生长Ni/Au顶电极506。
溅射靶材选用质量比纯度>99.99%的镍,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20-30cm3/秒、靶材基距为10cm和工作功率为20W~100W的条件下,制备顶电极镍,电极厚度为20nm~30nm。
溅射靶材选用质量比纯度>99.99%的Au,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4-1.3×10-3Pa、氩气流量为20-30cm3/秒、靶材基距为10cm和工作功率为20W-100W的条件下,制备栅电极金,电极厚度为150nm-200nm,之后在氮气或氩气环境下500
Figure PCTCN2017114675-appb-000002
火3min形成欧姆接触。
本发明的光电探测二极管采用了双异质结结构,从而形成双势垒,可有效降低漏电流,从而大幅提高光电二极管的器件可靠性,且本发明的实用性较高,目前在SiC衬底上进行同质外延和生长GaN层的工艺已成熟,也出现过在GaN衬底上生长Ga2O3的成熟工艺,本发明将两工艺结合,实用价值高。另外,本发明的光电探测二极管将Ga2O3材料应用于光吸收层,充分发挥其在紫外光探测方面的卓越性能,该材料在日盲区光透率可达80%以上,甚至 到90%,十分适合应用于光吸收层,此外其透明导电的电学特性也有利于提高光吸收层的光吸收能力,进而大幅提高光电探测二极管的器件性能。
【实施例二】
宽禁带半导体材料Ga2O3,因材料在日盲区的光透率可达80%甚至90%以上而极适合于深紫外光日盲区的光电探测,其光电灵敏度高,兼具蓝宝石的透明性与SiC的导电性,是光电器件尤其深紫外光探测器研究的理想半导体材料。
请参见图7及图8,图7为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的截面示意图,图8为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的俯视示意图。该APD探测二极管包括β-Ga2O3衬底701、N型同质外延层702、P层异质外延层703、顶电极704、底电极705。β-Ga2O3衬底701为无掺杂或掺杂Sn、Si、Al的β-Ga2O3(-201)、β-Ga2O3(010)或β-Ga2O3(001)材料;N型同质外延层702为掺杂Sn、Si、Al的β-Ga2O3层,掺杂浓度在1015cm-3量级;P型异质外延层703为Ir2O3层,掺杂浓度在1019-1020cm-3量级;顶电极704和底电极705为Au、Al、Ti、Sn、Ge、In、Ni、Co、Pt、W、Mo、Cr、Cu、Pb等金属材料、包含这些金属中2种以上合金或ITO等导电性化合物形成。另外,可以具有由不同的2种以上金属构成的2层结构,例如Al/Ti或者Ti/Au。
请参见图9,图9为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的制作方法流程示意图。该方法包括如下步骤:
步骤901、选取β-Ga2O3衬底;
步骤902、在β-Ga2O3衬底表面生长β-Ga2O3材料形成同质外延层;
步骤903、在同质外延层表面生长上分别生长Ir2O3材料形成异质外延层;
步骤904、刻蚀异质外延层和同质外延层形成梯形结构;
步骤905、在异质外延层表面形成顶电极;
步骤906、在β-Ga2O3衬底下表面形成底电极,最终形成APD探测器二极管。
对于步骤902,可以包括:
利用分子束外延工艺,在β-Ga2O3衬底表面生长掺杂浓度为1×1015~1×1016cm-3的N型β-Ga2O3材料以形成同质外延层;其中,同质外延层的厚度根据雪崩增益系数调节。
对于步骤903,可以包括:
利用CVD工艺,在同质外延层表面生长掺杂浓度为1×1019~1×1020cm-3的P型Ir2O3材料以形成异质外延层。
对于步骤904,可以包括:
步骤9041、采用第三光刻掩膜版,利用倾斜刻蚀工艺刻蚀异质外延层以在异质外延层内形成第一梯形结构;
步骤9042、采用第四光刻掩膜板,利用选择性倾斜刻蚀工艺刻蚀同质外延层以在同质外延层内形成第二梯形结构,以形成梯形结构。。
对于步骤905,可以包括:
采用第五光刻掩膜版,利用磁控溅射工艺在异质外延层表面溅射第一复合金属材料形成顶电极。
其中,利用磁控溅射工艺在异质外延层表面溅射第一复合金属材料,包括:
将Ti材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在异质外延层表面溅射形成Ti层;
将Au材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在Ti层表面溅射形成Au层,以形成第一复合金属材料。
对于步骤906,可以包括:
利用磁控溅射工艺在β-Ga2O3衬底下表面溅射第二复合金属材料形成底电极。
其中,利用磁控溅射工艺在β-Ga2O3衬底下表面溅射第二复合金属材料,包括:
将Ti材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在β-Ga2O3衬底下表面溅射形成Ti层;
将Au材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在Ti层表面溅射形成Au层,以形成第二复合金属材料。
另外,在步骤902之前,还包括:
步骤x1、将β-Ga2O3衬底分别在甲醇、丙酮和甲醇浸泡,之后采用去离子水和流动去离子水冲洗完成有机清洗;
步骤x2、将β-Ga2O3衬底在去离子水浸泡后在SPM溶液或者Piranha溶液中浸泡,之后在去离子水中浸泡并加热,冷却处理完成酸清洗。
本发明实施例,本发明首次提出了基于Ga2O3材料的新型紫外APD探测器的制备方法。本发明采用了Ga2O3材料,充分发挥该材料在深紫外光区域和可见光区域的极高光透率和透明度,该材料其远超SiC、GaN等材料的高禁带宽度等特性确保了APD探测器的耐压极高、击穿电场较高,使得本发明的新型紫外APD探测器比起之前的APD探测器更加适合高频、高辐射、高压等极端环境,该材料极优的热稳定性和化学稳定性在高温极端环境下器件可靠性相对以往APD探测器有所提高,其探测性能也将优于之前的APD探测器。
另外,通过调节结构中N/P型导电的Ga2O3层厚度可以调节雪崩增益系 数M,选择合适的M使得该发明的信噪比良好,具有较低的超额噪声,使器件达到最优光电探测灵敏度。
请参见图10a-图10g及图11a、图11b和图11c。图10a-图10g为本发明实施例提供的一种基于Ir2O3/Ga2O3的深紫外APD探测二极管的制作方法示意图;图11a为本发明实施例提供的一种第一光刻掩膜版的示意图,图11b为本发明实施例提供的一种第二光刻掩膜版的示意图,图11c为本发明实施例提供的一种第三光刻掩膜版的示意图。本实施例在上述实施例的基础上,对本发明的基于Ir2O3/Ga2O3的深紫外APD探测二极管的制作方法进行详细说明如下:
步骤1001:请参见图10a,准备衬底β-Ga2O3 1001,厚度为200μm-600μm,对衬底进行预处理清洗。
其中,衬底选用β-Ga2O31001理由:属于新一代超宽禁带半导体材料,其禁带宽度为4.7~4.9eV、理论击穿场强为8MV/cm,优于SiC和GaN传统宽禁带材料,此外其单晶衬底材料可以通过溶液法获得,制备成本较低。材料本身为透明状,具有较高的光透射率,因此采用β-Ga2O3制备的APD探测器对深紫外(波长范围200nm~280nm)探测更为敏感且工作偏置电压要求不高。。
对衬底先进行有机清洗,第一步甲醇浸泡3min,第二步丙酮浸泡3min,第三步甲醇浸泡3min,第四步去离子水冲洗3min,第五步流动去离子水清洗5min;
对衬底进行酸清洗,第一步去离子水浸泡并加热到90
Figure PCTCN2017114675-appb-000003
第二步用去离子水:30%过氧化氢:96%浓硫酸=1:1:4比例配制SPM溶液,SPM溶液浸泡5min,第二步或者用30%过氧化氢:98%浓硫酸=1:3比例配制Piranha溶液,Piranha溶液浸泡1min,第三步去离子水浸泡并加热到90
Figure PCTCN2017114675-appb-000004
之后冷却到室温。
衬底可选用200μm-600μm硅衬底热氧化1μm的SiO2替代,但替代后不需以上清洗步骤,改用RCA标准清洗,替代后绝缘效果变差,且制作过程更为复杂。
步骤1002:请参见图10b,在步骤1001所准备的β-Ga2O3衬底1001上通过分子束外延生长N型掺杂的β-Ga2O3材料形成同质外延层1002,掺杂元素可为Sn、Si、Al,掺杂浓度1015cm-3量级,在厚度在5-10um。
步骤1003:请参见图10c,在步骤1002所准备的N型同质外延层1002上通过CVD工艺生长P型掺杂区Ir2O3形成异质外延层1003,掺杂浓度1019~1020cm-3量级,厚度在5-10um。
步骤1004:请参见图10d及图11a,在步骤1003形成的整个衬底表面使用第三光刻掩膜版并通过倾斜刻蚀工艺在P型异质外延层1003中形成梯形结构;
步骤1005:请参见图10e及图11b,在步骤1004形成的整个衬底表面使用第四光刻掩膜版通过选择性倾斜刻蚀工艺在N型同质外延层1002中形成梯形结构;
具体地,倾斜刻蚀工艺即倾斜台面刻蚀工艺,具体工艺如下:首先采用BCl3基刻蚀气体进行ICP干法刻蚀5秒,随后在5%的HF溶液中浸泡10s;交替上述工艺进行循环,直至被刻蚀的材料被完全刻蚀。
步骤1006:请参见图10f及图11b,在步骤1005所准备的P型异质外延层1003上使用第五光刻掩膜版,通过磁控溅射生长顶电极Ti/Au;
具体地:溅射靶材选用质量比纯度>99.99%的Ti,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20~30cm3/秒、靶材基距为10cm和工作功率为100W的条件下,制备顶电极Ti,电极厚度为20nm-30nm。
溅射靶材选用质量比纯度>99.99%的Au,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20~30cm3/秒、靶材基距为10cm和工作功率为20W~100W的条件下,制备顶电极金,电极厚度为200nm~300nm,之后在氮气或氩气环境下500
Figure PCTCN2017114675-appb-000005
火3min形成欧姆接触。
步骤1007:请参见图10g,在衬底下表面通过磁控溅射生长底电极Ti/Au;
具体地,溅射靶材选用质量比纯度>99.99%的Ti,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4-1.3×10-3Pa、氩气流量为20-30cm3/秒、靶材基距为10cm和工作功率为100W的条件下,制备栅电极Ti,电极厚度为20nm-30nm。
溅射靶材选用质量比纯度>99.99%的Au,以质量百分比纯度为99.999%的Ar作为溅射气体通入溅射腔,溅射前,用高纯氩气对磁控溅射设备腔体进行5分钟清洗,然后抽真空。在真空度为6×10-4~1.3×10-3Pa、氩气流量为20~30cm3/秒、靶材基距为10cm和工作功率为20W~100W的条件下,制备栅电极金,电极厚度为200nm~300nm,之后在氮气或氩气环境下500
Figure PCTCN2017114675-appb-000006
火3min形成欧姆接触。
本发明的紫外APD探测器首次采用了光学性能卓越的Ga2O3材料,充分发挥该材料在深紫外光区域和可见光区域的极高光透率和透明度,该材料在深紫外光区域光透率可达80%以上,此外该材料的电学特性确保了本发明的新型紫外APD探测器的耐压极高、击穿电场较高,其远超SiC、GaN等材料的高禁带宽度使得本发明的新型紫外APD探测器比起目前的APD探测器更加适合高频、高辐射、高温高压等极端环境,在极端环境下不仅器件可靠性大幅提高,探测性能也将优于目前的APD探测器。另外,本发明的新型紫外 APD探测器的器件结构是在传统APD探测器,即雪崩光电二极管的基础上加以改进,可有效提高体雪崩击穿电压从而提高雪崩增益系数M,同时通过调节结构中N/P型导电的Ga2O3层厚度可以调节M,选择合适的M使得该发明的信噪比良好,具有较低的超额噪声,使器件达到最优光电探测灵敏度。
以上,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
工业实用性
本发明实施例通过在光电探测器的结构中使用Ga2O3材料,充分发挥了该材料在深紫外光区域和可见光区域的极高光透率和透明度,可以大幅提高光电探测二极管的器件性能。

Claims (14)

  1. 一种基于Ga2O3材料的紫外光电探测器的制备方法,其特征在于,包括:
    选取衬底;
    在所述衬底上表面形成Ga2O3层;
    在所述Ga2O3层上形成顶电极;
    在所述衬底下表面形成底电极。
  2. 如权利要求1所述的制备方法,其特征在于,选取衬底,包括:
    选取厚度为200μm-600μm的β-Ga2O3材料作为所述衬底。
  3. 如权利要求2所述的制备方法,其特征在于,在所述衬底上形成Ga2O3层,包括:
    利用分子束外延工艺,在所述衬底表面生长掺杂浓度为1×1015~1×1016cm-3的N型β-Ga2O3材料以形成所述Ga2O3层。
  4. 如权利要求3所述的制备方法,其特征在于,在所述衬底上形成Ga2O3层之后,还包括:
    利用CVD工艺,在所述Ga2O3层表面生长掺杂浓度为1×1019~1×1020cm-3的P型Ir2O3材料以形成Ir2O3层;
    采用第一光刻掩膜版,利用倾斜刻蚀工艺刻蚀所述Ir2O3层以在所述Ir2O3层内形成第一梯形结构;
    采用第二光刻掩膜板,利用选择性倾斜刻蚀工艺刻蚀所述Ga2O3层以在所述Ga2O3层内形成第二梯形结构。
  5. 如权利要求4所述的制备方法,其特征在于,在所述Ga2O3层上形成顶电极,包括:
    采用第三光刻掩膜版,利用磁控溅射工艺在所述Ga2O3层表面溅射第一复合金属材料形成所述顶电极。
  6. 如权利要求2所述的制备方法,其特征在于,在所述衬底下表面生长底电极,包括:
    将Ti材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在β-Ga2O3衬底下表面溅射形成Ti层;
    将Au材料作为溅射靶材,以Ar气体作为溅射气体通入溅射腔内,在真空度为6×10-4~1.3×10-3Pa,工作频率为100W的条件下,在所述Ti层表面溅射形成Au层,以形成第二复合金属材料以形成所述底电极。
  7. 如权利要求1所述的制备方法,其特征在于,选取衬底,包括:
    选取N型的4H-SiC或6H-SiC材料作为所述衬底;
    利用RCA标准清洗工艺对所述衬底进行清洗。
  8. 如权利要求7所述的制备方法,其特征在于,在所述衬底上形成Ga2O3层之前,还包括:
    利用LPCVD工艺,在所述衬底表面生长掺杂N元素的SiC材料以形成N型的同质外延层;
    采用MOCVD工艺,在所述同质外延表面生长掺杂N元素的GaN材料以形成所述GaN层。
  9. 如权利要求8所述的制备方法,其特征在于,在所述衬底上形成Ga2O3层,包括:
    利用MBE工艺,在所述GaN层表面生长β-Ga2O3材料形成所述Ga2O3层。
  10. 如权利要求9所述的制备方法,其特征在于,在所述衬底上形成Ga2O3层之后,还包括:
    以Ni材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为100W,真空度为6×10-4~1.3×10-3Pa的条件下,在所述Ga2O3层表面溅射 Ni材料以形成光吸收层。
  11. 如权利要求10所述的制备方法,其特征在于,在所述Ga2O3层上形成顶电极,包括:
    以Ni材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为20~100W,在真空度为6×10-4~1.3×10-3Pa的条件下,在所述Ga2O3层表面溅射形成Ni材料;
    以Au材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为20~100W,在真空度为6×10-4~1.3×10-3Pa的条件下,在Ni材料表面溅射Au材料形成Ni/Au叠层双金属材料以形成所述顶电极。
  12. 如权利要求11所述的制备方法,其特征在于,在所述Ga2O3层上形成顶电极,还包括:
    在氮气和氩气的气氛下,利用快速热退火工艺在所述Ga2O3层与顶电极的表面处形成欧姆接触。
  13. 如权利要求10所述的制备方法,其特征在于,在所述衬底下表面生长底电极,包括:
    以Ni材料作为靶材,以氩气作为溅射气体通入溅射腔体中,在工作功率为100W,真空度为6×10-4~1.3×10-3Pa的条件下,在所述衬底的下表面溅射Ni材料以形成所述底电极。
  14. 如权利要求13所述的制备方法,其特征在于,在所述衬底下表面生长底电极,还包括:
    在氮气和氩气的气氛下,利用快速热退火工艺在所述整个衬底的下表面与底电极之间处形成欧姆接触。
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