CN108519411A - A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity - Google Patents
A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity Download PDFInfo
- Publication number
- CN108519411A CN108519411A CN201810298037.5A CN201810298037A CN108519411A CN 108519411 A CN108519411 A CN 108519411A CN 201810298037 A CN201810298037 A CN 201810298037A CN 108519411 A CN108519411 A CN 108519411A
- Authority
- CN
- China
- Prior art keywords
- type
- electrode
- nitride semiconductor
- wafer
- activation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000004065 semiconductor Substances 0.000 title claims abstract description 48
- 230000004913 activation Effects 0.000 title claims abstract description 34
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 238000013461 design Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 3
- 238000001994 activation Methods 0.000 claims description 35
- 239000000523 sample Substances 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- -1 H 2 CO 3 Chemical compound 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 abstract description 38
- 229910002704 AlGaN Inorganic materials 0.000 abstract description 28
- 230000005693 optoelectronics Effects 0.000 abstract description 10
- 238000000137 annealing Methods 0.000 abstract description 8
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 4
- 238000012993 chemical processing Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000008393 encapsulating agent Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000370 acceptor Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000013074 reference sample Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910019080 Mg-H Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000000344 low-energy electron-beam lithography Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 102100021164 Vasodilator-stimulated phosphoprotein Human genes 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 108010054220 vasodilator-stimulated phosphoprotein Proteins 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Weting (AREA)
Abstract
Description
技术领域technical field
本发明涉及III族氮化物半导体材料,尤其是涉及一种氮化物半导体材料除氢激活提升p型导电性的方法。The invention relates to III-group nitride semiconductor materials, in particular to a method for dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity.
背景技术Background technique
氮化物半导体材料因其直接带隙可调范围广、结构稳定性好及临界击穿电压高等独特的优势,成为制备短波长高亮度发光二极管、高功率激光器、高灵敏度光探测器以及高温大功率电子器件的材料基础。过去的十多年间,在众多的研究工作者及产业界持续不断的共同努力下,可见蓝绿光、紫外、深紫外光电子器件获得了极大的发展。然而与GaN基的可见光和近紫外光电子器件相比,AlGaN紫外光电子器件的工作效率还普遍较低,其关键的原因在于AlGaN材料体系的本质特性以及器件工艺方面所存在的难以克服的科学难题,包括高Al组分AlGaN材料外延晶体质量不高、高Al组分AlGaN材料的光学各项异性、自发极化及压电极化较强,以及p型掺杂和激活困难等。Nitride semiconductor materials, due to their unique advantages such as wide adjustable range of direct bandgap, good structural stability and high critical breakdown voltage, have become the ideal choice for the preparation of short-wavelength high-brightness light-emitting diodes, high-power lasers, high-sensitivity photodetectors and high-temperature high-power Materials basis for electronic devices. In the past ten years, with the continuous joint efforts of many researchers and the industry, visible blue-green light, ultraviolet, and deep ultraviolet optoelectronic devices have achieved great development. However, compared with GaN-based visible light and near-ultraviolet optoelectronic devices, the work efficiency of AlGaN ultraviolet optoelectronic devices is generally lower. The key reason is the essential characteristics of AlGaN material system and the insurmountable scientific problems in the device process. Including high Al composition AlGaN material epitaxial crystal quality is not high, optical anisotropy, spontaneous polarization and piezoelectric polarization of high Al composition AlGaN material are strong, and p-type doping and activation are difficult.
掺杂作为调控半导体导电性质最重要的手段之一,在半导体器件的制备当中扮演着关键的角色。目前III族氮化物半导体材料的n型掺杂效率较高,能够提供较高的电子浓度,满足各种光电子器件的使用要求。与n型掺杂相比,目前III族氮化物半导体材料的p型掺杂效率普遍不高,尤其在高Al组分的AlGaN材料中,p型杂质容易形成深能级,受主激活能高,杂质的激活效率较低,导致p型AlGaN材料的导电性通常处于较低水平,无法满足各类光电子器件的使用要求。而且在材料生长过程中所引入的H原子容易与p型杂质结合形成络合物,进而钝化p型杂质的受主活性,减小材料的空穴浓度,进一步降低了AlGaN材料的p型导电性。Doping, as one of the most important means to control the conductive properties of semiconductors, plays a key role in the preparation of semiconductor devices. At present, the n-type doping efficiency of III-nitride semiconductor materials is relatively high, which can provide relatively high electron concentration and meet the requirements of various optoelectronic devices. Compared with n-type doping, the p-type doping efficiency of Group III nitride semiconductor materials is generally not high, especially in AlGaN materials with high Al composition, p-type impurities are easy to form deep energy levels, and the acceptor activation energy is high. , The activation efficiency of impurities is low, resulting in the low level of electrical conductivity of p-type AlGaN materials, which cannot meet the requirements of various optoelectronic devices. Moreover, the H atoms introduced during the material growth process are easy to combine with p-type impurities to form complexes, thereby passivating the acceptor activity of p-type impurities, reducing the hole concentration of the material, and further reducing the p-type conductivity of AlGaN materials. sex.
为了提高p型氮化物材料的导电性,研究者提出了许多方法,包括极化诱导掺杂、超晶格掺杂、delta掺杂及受主-施主共掺等等。针对H原子钝化p型杂质受主活性的难题,1989年日本的Amano研究组(Amano H et al,Japanese Journal of Applied Physics,1989,28(12A):L2112)通过低能电子束辐照工艺,打断p型杂质Mg与H之间的键连,除去H,恢复了Mg杂质的受主活性,首次获得了p型的GaN样品。随后,1992年日本Nakamura研究组(Nakamura S et al,Japanese Journal of Applied Physics,1992,31(2B):L139.)发现在氮气气氛中热退火能够起到和低能电子束辐照同样的除H效果,且能更方便地获得高导电性的p型GaN材料。跟GaN相比,AlGaN材料的p型激活难度更大,需要更高的退火温度。尽管退火目前已经成为p型AlGaN材料最常用的激活方法,但由于其需要用到800℃以上的高温,容易在激活的同时形成氮空位等缺陷补偿中心,降低空穴浓度,导致难以得到一个最佳的激活效果,限制了p型AlGaN材料导电性的进一步提高。In order to improve the conductivity of p-type nitride materials, researchers have proposed many methods, including polarization-induced doping, superlattice doping, delta doping, and acceptor-donor co-doping and so on. Aiming at the problem of H atom passivation of p-type impurity acceptor activity, in 1989, the Amano research group in Japan (Amano H et al, Japanese Journal of Applied Physics, 1989, 28(12A): L2112) used a low-energy electron beam irradiation process, Break the bond between the p-type impurity Mg and H, remove H, restore the acceptor activity of the Mg impurity, and obtain the p-type GaN sample for the first time. Subsequently, in 1992, the Japanese Nakamura research group (Nakamura S et al, Japanese Journal of Applied Physics, 1992, 31(2B): L139.) found that thermal annealing in a nitrogen atmosphere can achieve the same H removal as low-energy electron beam irradiation. effect, and it is more convenient to obtain high-conductivity p-type GaN materials. Compared with GaN, the p-type activation of AlGaN material is more difficult and requires a higher annealing temperature. Although annealing has become the most commonly used activation method for p-type AlGaN materials, it is easy to form defect compensation centers such as nitrogen vacancies during activation and reduce the hole concentration because it requires high temperatures above 800 °C, making it difficult to obtain an optimal activation method. The best activation effect limits the further improvement of the conductivity of p-type AlGaN materials.
针对上述提到的问题,本发明提出了一种新型的氮化物半导体材料p型导电性激活提升方法,主要采用恒电位电化学处理打断p型杂质与H的键连,并利用电势梯度和除氢溶剂中的离子活性将H从样品中移除,激活p型杂质的受主活性,提高空穴浓度,改善氮化物半导体材料的p型导电性。此方法装置简单、操作简便、常温工作、不会引进额外的缺陷,可制备出具有良好导电特性的p型氮化物半导体材料,且可对已制备的完整器件结构晶圆片做后期处理,适用大规模的工业化推广,在紫外、深紫外LED、LD、探测器等光电子领域中有着广泛的应用前景和开发潜力。In view of the problems mentioned above, the present invention proposes a novel method for activating and improving the p-type conductivity of nitride semiconductor materials, which mainly uses constant potential electrochemical treatment to break the bond between p-type impurities and H, and utilizes the potential gradient and The ion activity in the dehydrogenation solvent removes H from the sample, activates the acceptor activity of p-type impurities, increases the hole concentration, and improves the p-type conductivity of the nitride semiconductor material. This method is simple in equipment, easy to operate, works at room temperature, does not introduce additional defects, can prepare p-type nitride semiconductor materials with good electrical conductivity, and can do post-processing on the prepared wafers with complete device structures. Large-scale industrial promotion has broad application prospects and development potential in optoelectronic fields such as ultraviolet and deep ultraviolet LEDs, LDs, and detectors.
发明内容Contents of the invention
本发明旨在针对目前氮化物半导体材料p型掺杂效率低的难题,提供操作简便、无需高温退火,可制备具有良好导电特性的p型GaN和AlGaN材料,并且可对完整结构器件晶圆片做后期处理,在可见光、紫外、深紫外的LED、LD、探测器等光电子领域中有着广泛的应用前景和开发潜力的一种氮化物半导体材料除氢激活提升p型导电性的方法。The present invention aims at solving the problem of low p-type doping efficiency of nitride semiconductor materials at present, and provides p-type GaN and AlGaN materials with easy operation, no need for high-temperature annealing, good electrical conductivity, and complete structure device wafers. After post-processing, it has broad application prospects and development potential in visible light, ultraviolet, deep ultraviolet LED, LD, detector and other optoelectronic fields. It is a method for dehydrogenation activation of nitride semiconductor materials to improve p-type conductivity.
本发明包括以下步骤:The present invention comprises the following steps:
1)设计三电极电化学处理装置;1) Design a three-electrode electrochemical treatment device;
2)将p型掺杂的半导体晶片密封至容器底部,作为工作电极;2) sealing the p-type doped semiconductor wafer to the bottom of the container as a working electrode;
3)设置一个辅助电极和一个参比电极,与工作电极构成电化学三电极系统;3) An auxiliary electrode and a reference electrode are set to form an electrochemical three-electrode system with the working electrode;
4)选择除氢电解液,加入容器中,并淹没三电极;4) Select the hydrogen removal electrolyte, add it to the container, and submerge the three electrodes;
5)于工作电极和辅助电极之间施加直流偏压,进行除H并激活p型杂质;5) Apply a DC bias voltage between the working electrode and the auxiliary electrode to remove H and activate p-type impurities;
6)激活处理完毕,取出p型半导体晶片,进行去离子水超声清洗;6) After the activation process is completed, take out the p-type semiconductor wafer and perform ultrasonic cleaning with deionized water;
7)利用电学装置测试晶片的电学性质。7) Using an electrical device to test the electrical properties of the wafer.
在步骤1)中,所述三电极电化学处理装置可采用平板电解池,其主体为特弗龙材料或石英材料所制成的容器,容器底部设置一个开口,用于除氢电解液与p型半导体晶片的接触,开口与晶片之间用氟胶O圈进行密封,以避免电解液的泄露,容器底部开口的大小由所处理的晶片尺寸所决定,原则上开口比晶片尺寸略小一些,以留出部分晶片区域与外部电源进行连接。为了改善p型半导体工作电极与外部电源的电接触,可在晶片上制作金属电极,或使用铟作为探针与晶片的接触金属,以减小接触电阻,提高电化学除氢激活的效率;参比电极与辅助电极固定并密封于容器侧壁,参比电极与辅助电极皆与p型工作电极呈平行放置;只要改变尺寸,此装置可以处理不同大小的晶片,小至几厘米,大至完整2inch、4inch甚至更大尺寸的完整器件结构晶圆片。In step 1), the three-electrode electrochemical treatment device can adopt a flat electrolytic cell, the main body of which is a container made of Teflon material or quartz material, and an opening is arranged at the bottom of the container for dehydrogenation electrolyte and p The contact between the opening and the wafer is sealed with a fluorine rubber O-ring to avoid leakage of the electrolyte. The size of the opening at the bottom of the container is determined by the size of the wafer being processed. In principle, the opening is slightly smaller than the size of the wafer. To reserve a part of the chip area to connect with the external power supply. In order to improve the electrical contact between the p-type semiconductor working electrode and the external power supply, metal electrodes can be made on the wafer, or indium can be used as the contact metal between the probe and the wafer to reduce the contact resistance and improve the efficiency of electrochemical dehydrogenation activation; see The reference electrode and the auxiliary electrode are fixed and sealed on the side wall of the container, and the reference electrode and the auxiliary electrode are placed parallel to the p-type working electrode; as long as the size is changed, this device can handle wafers of different sizes, as small as a few centimeters, as large as a complete Complete device structure wafers of 2inch, 4inch or even larger sizes.
在步骤2)中,所述p型掺杂的氮化物半导体的元素包括Mg、Zn、Cd、Be、Ca、Ba等中的至少两种;所述p型掺杂的氮化物半导体的结构可采用单层、多层、超晶格及组分渐变等结构,包含p型层的完整LED、LD、探测器等复杂器件结构同样在此所陈述的范围之内。In step 2), the elements of the p-type doped nitride semiconductor include at least two of Mg, Zn, Cd, Be, Ca, Ba, etc.; the structure of the p-type doped nitride semiconductor can be The use of single-layer, multi-layer, superlattice and composition gradient structures, including complex device structures such as p-type layers such as LEDs, LDs, and detectors, is also within the scope of this statement.
在步骤3)中,所述电化学三电极系统的辅助电极包括铂、铅、铜、钛、锡和石墨等不溶于电解液的惰性导电材料,参比电极包括饱和甘汞电极(SCE)、Ag/AgCl电极和标准氢电极(SHE或NHE)等。In step 3), the auxiliary electrode of the electrochemical three-electrode system includes platinum, lead, copper, titanium, tin and graphite and other insoluble inert conductive materials in the electrolyte, and the reference electrode includes a saturated calomel electrode (SCE), Ag/AgCl electrode and standard hydrogen electrode (SHE or NHE), etc.
在步骤4)中,所述除氢电解液的种类包括各类酸、碱及中性溶液,可选自HCl、HF、HBr、HI、H2SO4、H2CO3、NaOH、KOH、Ca(OH)2等中的一种;电解液的浓度是成功进行除氢并激活p型杂质活性、改善p型导电性的关键参数之一,应根据所处理的p型半导体晶片、电解液类型及其他实验条件之不同,配制合适浓度之电解液。In step 4), the type of hydrogen removal electrolyte includes various acids, alkalis and neutral solutions, which can be selected from HCl, HF, HBr, HI, H 2 SO 4 , H 2 CO 3 , NaOH, KOH, One of Ca(OH) 2 , etc.; the concentration of the electrolyte is one of the key parameters for successfully removing hydrogen and activating the activity of p-type impurities and improving the p-type conductivity. Depending on the type and other experimental conditions, prepare an electrolyte with a suitable concentration.
在步骤5)中,所述直流偏压大小及电化学处理持续时间也是影响实验结果的两个关键参数,应根据所处理的p型半导体晶片成分、结构、厚度,p型掺杂元素,电解液的类型和浓度,以及其他实验条件之不同,选用合适的偏压大小及持续时间,打断p型杂质与H的键连,利用电势梯度,使生成的H+离子扩散至材料的表面并与电解液中的离子相结合以脱离样品,即可激活半导体中的p型掺杂受主活性,提高样品空穴浓度,进而改善其p型导电性。In step 5), the magnitude of the DC bias and the duration of the electrochemical treatment are also two key parameters that affect the experimental results, and should be based on the processed p-type semiconductor wafer composition, structure, thickness, p-type doping elements, electrolytic Depending on the type and concentration of the liquid, as well as other experimental conditions, select the appropriate bias size and duration to break the bond between the p-type impurity and H, and use the potential gradient to diffuse the generated H + ions to the surface of the material and Combining with ions in the electrolyte to separate from the sample can activate the p-type doping acceptor activity in the semiconductor, increase the hole concentration of the sample, and then improve its p-type conductivity.
本发明的关键是:The key of the present invention is:
1)三电极电化学装置的主体容器由特弗龙材料或石英材料所制作,容器底部设置一个开口,用于除氢电解液与p型半导体晶片的接触,开口与晶片之间用氟胶O圈密封,参比电极与辅助电极固定并密封于容器侧壁,二者皆与p型工作电极呈平行放置。1) The main container of the three-electrode electrochemical device is made of Teflon material or quartz material. There is an opening at the bottom of the container for the contact between the dehydrogenation electrolyte and the p-type semiconductor wafer. Fluorine rubber O is used between the opening and the wafer. The ring is sealed, the reference electrode and the auxiliary electrode are fixed and sealed on the side wall of the container, and both are placed in parallel with the p-type working electrode.
不论所处理的样品为单纯的p型结构,还是包含p型层的完整器件晶片,装置的此种结构设计保证了电解液只与晶片中的p型层表面相接触。当样品为结构复杂的LED、LD、探测器等完整器件时,由于n型层、有源层等复杂结构的存在,若整个样品都与电解液相接触,外加电压及回路的电流会不稳定,导致最终的p型层激活效果欠佳。仅使p型层表面与电解液相接触,可排除n型层、有源层等复杂结构对电势、电流的影响,保证了最佳的p型层激活效果。Regardless of whether the processed sample is a pure p-type structure or a complete device wafer including a p-type layer, the structural design of the device ensures that the electrolyte only contacts the surface of the p-type layer in the wafer. When the sample is a complete device with complex structure such as LED, LD, detector, etc., due to the existence of complex structures such as n-type layer and active layer, if the entire sample is in contact with the electrolyte, the applied voltage and the current of the circuit will be unstable. , resulting in poor activation of the final p-type layer. Only making the surface of the p-type layer in contact with the electrolyte can eliminate the influence of complex structures such as n-type layer and active layer on the potential and current, and ensure the best activation effect of the p-type layer.
2)外接导线或探针与作为工作电极的p型晶片接触时,为了减小接触势垒的影响,可在晶片表面制作金属电极,或使用铟作为接触金属,改善其电接触。2) When the external wire or probe is in contact with the p-type wafer as the working electrode, in order to reduce the influence of the contact barrier, metal electrodes can be made on the wafer surface, or indium can be used as the contact metal to improve its electrical contact.
3)辅助电极可使用铂、铅、铜、钛、锡或石墨等不溶于电解液的惰性导电材料,其形状应为片状,具有较大的表面积,以使外部所加极化主要作用于工作电极上,且与p型晶片工作电极要呈平行放置,以尽量提高电化学处理的整体均匀型。3) The auxiliary electrode can use platinum, lead, copper, titanium, tin or graphite and other inert conductive materials that are insoluble in the electrolyte, and its shape should be flake with a large surface area so that the external polarization mainly acts On the working electrode, and placed parallel to the working electrode of the p-type wafer, in order to improve the overall uniformity of the electrochemical treatment as much as possible.
4)参比电极用于测定工作电极的电势,应具有良好的电势稳定性和重现性,可使用饱和甘汞电极(SCE)、Ag/AgCl电极或标准氢电极(SHE或NHE)等材料。4) The reference electrode is used to measure the potential of the working electrode. It should have good potential stability and reproducibility. Materials such as saturated calomel electrode (SCE), Ag/AgCl electrode or standard hydrogen electrode (SHE or NHE) can be used .
5)除氢电解液的种类及浓度是实验的关键参数。本发明选用各类酸、碱或中性溶液,如HCl、HF、HBr、HI、H2SO4、H2CO3、NaOH、KOH、Ca(OH)2等,或其中至少两种溶液之混合,根据p型半导体晶片的成分、结构、厚度以及其他实验条件的不同,配成不同浓度之电解液。电解液浓度太低,除H的效率不高,浓度过高,在外加电压的共同作用下,晶片表面易被溶液所腐蚀。以HCl溶液为例,5V的外加电压下,溶液浓度在1.0M时,除氢效果、实验重复型最佳,并且不破坏晶片的原有结构。5) The type and concentration of hydrogen removal electrolyte are the key parameters of the experiment. The present invention selects various acid, alkali or neutral solutions, such as HCl, HF, HBr, HI, H 2 SO 4 , H 2 CO 3 , NaOH, KOH, Ca(OH) 2, etc., or at least two of them Mixing, according to the composition, structure, thickness and other experimental conditions of the p-type semiconductor wafer, make electrolytes with different concentrations. If the concentration of the electrolyte is too low, the efficiency of removing H is not high, and if the concentration is too high, the surface of the wafer is easily corroded by the solution under the combined action of the applied voltage. Taking HCl solution as an example, under the applied voltage of 5V, when the solution concentration is 1.0M, the hydrogen removal effect and the experimental repeatability are the best, and the original structure of the wafer will not be damaged.
6)所加偏压大小一般控制在0~10V,持续时间一般控制在0~20min。偏压及处理时间也是实验的两个关键参数,过低的偏压和太短的处理时间,激活效果无法达到最佳,过高的偏压和过长的处理时间,会对晶片表面造成一定腐蚀和损伤。实际操作时,应根据p型晶片的成分、结构、厚度,p型掺杂元素,电解液的类型和浓度,以及其他实验条件的不同,选用合适的偏压大小及持续时长进行电化学p型导电性激活处理,即可获得最佳的激活效果,提高p型半导体材料的导电性。以GaN材料为例,电解液为1M浓度的HCl时,外加电压为4V左右、持续时间为5min左右时,激活效果最好。当样品Al组分增加时,可适当提高外加电压,如Al组分为40%左右的样品,外加电压为6V左右时激活效果最佳。6) The applied bias voltage is generally controlled at 0-10V, and the duration is generally controlled at 0-20min. Bias voltage and processing time are also two key parameters of the experiment. If the bias voltage is too low and the processing time is too short, the activation effect cannot be optimal. If the bias voltage is too high and the processing time is too long, it will cause certain damage to the wafer surface. corrosion and damage. In actual operation, according to the composition, structure, thickness of the p-type wafer, p-type doping elements, type and concentration of electrolyte, and other experimental conditions, select the appropriate bias voltage and duration for electrochemical p-type The conductivity activation treatment can obtain the best activation effect and improve the conductivity of the p-type semiconductor material. Taking GaN material as an example, when the electrolyte is HCl with a concentration of 1M, the activation effect is the best when the applied voltage is about 4V and the duration is about 5min. When the Al composition of the sample increases, the applied voltage can be appropriately increased. For example, for a sample with an Al composition of about 40%, the activation effect is the best when the applied voltage is about 6V.
利用以上关键点设计实验方案,构造电化学三电极实验设备,对p型氮化物半导体材料进行除H、激活处理,极大地降低了样品的电阻率,增加了空穴浓度,提高了其导电性,取得了良好的预期效果。Using the above key points to design the experimental plan, construct the electrochemical three-electrode experimental equipment, and perform H removal and activation treatment on the p-type nitride semiconductor material, which greatly reduces the resistivity of the sample, increases the hole concentration, and improves its conductivity. , and achieved good expected results.
本发明利用外加电压打断p型杂质与H的键连,并利用电势梯度和除氢溶剂中的离子活性将H从样品中移除,激活p型杂质受主活性,提高氮化物半导体材料p型导电性能,可广泛应用于GaN基、AlGaN基的各类电子、光电子器件。In the present invention, an external voltage is used to break the bonding between p-type impurities and H, and the potential gradient and the ion activity in the hydrogen removal solvent are used to remove H from the sample, thereby activating the activity of p-type impurity acceptors and improving the p-type of the nitride semiconductor material. Type conductivity, can be widely used in various electronic and optoelectronic devices based on GaN and AlGaN.
本发明操作简便、无需高温退火,可制备出具有良好导电特性的p型GaN和AlGaN材料,并且可对完整结构器件晶圆片做后期处理,在可见光、紫外、深紫外的LED、LD、探测器等光电子领域中有着广泛的应用前景和开发潜力。The invention is easy to operate, does not require high-temperature annealing, can prepare p-type GaN and AlGaN materials with good electrical conductivity, and can perform post-processing on complete structure device wafers, and can be used in visible light, ultraviolet, deep ultraviolet LED, LD, detection It has broad application prospects and development potential in optoelectronic fields such as devices.
附图说明Description of drawings
图1为用于氮化物半导体材料p型导电性激活提升的电化学三电极实验设备示意图;Fig. 1 is a schematic diagram of an electrochemical three-electrode experimental equipment used to activate and enhance the p-type conductivity of nitride semiconductor materials;
图2为经过不同电压电化学处理之后p型AlGaN样品的IV曲线图;Figure 2 is the IV curves of p-type AlGaN samples after electrochemical treatment at different voltages;
图3为经过不同电压电化学处理之后p型AlGaN样品的电阻率大小;Figure 3 shows the resistivity of p-type AlGaN samples after electrochemical treatment with different voltages;
图4为p型GaN表面H+离子与盐酸溶液中Cl-离子结合并脱离样品的过程示意图;Figure 4 is a schematic diagram of the process in which H + ions on the surface of p-type GaN combine with Cl- ions in hydrochloric acid solution and leave the sample;
图5为经过不同电压电化学处理之后p型AlGaN样品的SIMS元素分布图。Fig. 5 is a SIMS element distribution diagram of a p-type AlGaN sample after electrochemical treatment at different voltages.
具体实施方式Detailed ways
以下结合详细附图,以实施例进一步对本发明的实施方式和步骤作具体说明。Below in conjunction with the detailed drawings, the embodiments and steps of the present invention will be further described in detail with examples.
1、用于氮化物半导体材料p型导电性激活提升的电化学三电极实验装置1. An electrochemical three-electrode experimental device for activation and enhancement of p-type conductivity of nitride semiconductor materials
首先,设计并制作用于氮化物半导体材料p型导电性激活提升的电化学三电极实验装置。如图1所示,本实施例中所使用的电化学三电极装置主体容器1由特氟龙材料制成,容器1底部设置一个开口2用于工作电极3与电解液4的接触,开口2用氟胶O圈密封,工作电极3与容器1之间可用一卡扣卡紧。辅助电极5为铂片(Pt plate),参比电极6为饱和甘汞电极(SCE),二者分别固定并密封于容器1侧壁。三个电极呈平行放置,以尽量保证电化学处理的整体均匀性。工作电极与外部电源之间用一带有伸缩弹簧的探针7和导线8相连,在探针7与p型工作电极之间用铟金属9改善电接触。First, design and fabricate an electrochemical three-electrode experimental device for activation and promotion of p-type conductivity of nitride semiconductor materials. As shown in Figure 1, the main body container 1 of the electrochemical three-electrode device used in this embodiment is made of Teflon material, and an opening 2 is arranged at the bottom of the container 1 for the contact of the working electrode 3 and the electrolyte 4, and the opening 2 It is sealed with a fluorine rubber O-ring, and a buckle can be used to fasten the working electrode 3 and the container 1. The auxiliary electrode 5 is a platinum plate (Pt plate), and the reference electrode 6 is a saturated calomel electrode (SCE), which are respectively fixed and sealed on the side wall of the container 1 . The three electrodes are placed in parallel to ensure the overall uniformity of the electrochemical treatment as much as possible. A probe 7 with a stretch spring is connected to a wire 8 between the working electrode and the external power supply, and indium metal 9 is used between the probe 7 and the p-type working electrode to improve electrical contact.
2、电化学三电极实验装置制作完毕,进入实验的准备阶段2. The electrochemical three-electrode experimental device is completed and enters the preparation stage of the experiment
1)本实施例中所处理的p型AlGaN晶片由MOCVD所外延生长,其平均组分约为40%。将晶片密封至容器底部作为工作电极,并用卡扣将晶片与容器之间卡紧。卡扣卡紧后,带有伸缩弹簧的探针7、铟接触金属9与p型半导体晶片三者形成良好的电接触。1) The p-type AlGaN wafer processed in this embodiment is epitaxially grown by MOCVD, and its average composition is about 40%. The wafer is sealed to the bottom of the container as the working electrode, and the wafer and the container are fastened with buckles. After the buckle is fastened, the probe 7 with the telescopic spring, the indium contact metal 9 and the p-type semiconductor chip form a good electrical contact.
2)使用导线8将三个电极与外部直流电源相连接,以构成电化学三电极实验系统。2) Using wires 8 to connect the three electrodes with an external DC power supply to form an electrochemical three-electrode experimental system.
3)制备浓度为1.0M的HCl溶液作为除氢电解液,并将其加入容器中,直至完全淹没三电极。3) Prepare a HCl solution with a concentration of 1.0M as the hydrogen removal electrolyte, and add it into the container until the three electrodes are completely submerged.
3、进入实验反应阶段,除H激活并提升晶片p型导电性3. Enter the experimental reaction stage, remove H to activate and improve the p-type conductivity of the wafer
以上实验准备工作都完成后,用外部电源在工作电极和辅助电极之间施加一直流偏压,进入实验反应阶段,开始除H激活并提升AlGaN晶片p型导电性,持续一段时间。本实施例分别在不同的条件下对p型AlGaN晶片进行电化学激活处理,其中三个样品所加偏压大小分别为2V、4V和6V,持续时间都为5min。另有一个样品未经电化学处理,作为参考样品,以考察电化学处理所产生的影响。三电极恒电位电化学处理实验条件如表1所示。After the above experimental preparations are completed, an external power supply is used to apply a DC bias voltage between the working electrode and the auxiliary electrode to enter the experimental reaction stage, and start to remove H to activate and improve the p-type conductivity of the AlGaN wafer for a period of time. In this embodiment, p-type AlGaN wafers are subjected to electrochemical activation treatment under different conditions, in which the bias voltages applied to the three samples are 2V, 4V and 6V respectively, and the duration is 5 minutes. Another sample without electrochemical treatment was used as a reference sample to investigate the effect of electrochemical treatment. The experimental conditions of the three-electrode constant potential electrochemical treatment are shown in Table 1.
表1Table 1
4、激活处理完毕,取出晶片并清洗4. After the activation process is completed, take out the wafer and clean it
电化学激活处理结束后,将电解液倒出,取下p型AlGaN晶片,并将晶片浸泡于去离子水中用超声清洗十min,之后将晶片置于烘烤台上烘干,以去除掉样品表面所残留的电解液和去离子水。After the electrochemical activation treatment, pour out the electrolyte, remove the p-type AlGaN wafer, soak the wafer in deionized water and clean it ultrasonically for ten minutes, then place the wafer on a baking table to dry to remove the sample Electrolyte and deionized water remaining on the surface.
5、欧姆接触金属电极制作5. Fabrication of ohmic contact metal electrodes
晶片清洗完毕后,使用磁控溅射的方法在样品上镀40nm的Ni金属作为电极,在氮气氛围中、480℃的温度下,经过15min的热退火之后,Ni金属和p型AlGaN样品之间形成了良好的欧姆接触,为后续电学性质测试的可靠和稳定提供了保证。After the wafer was cleaned, 40nm Ni metal was plated on the sample as an electrode by magnetron sputtering. After 15 min of thermal annealing at 480°C in a nitrogen atmosphere, the gap between the Ni metal and the p-type AlGaN sample was A good ohmic contact is formed, which provides a guarantee for the reliability and stability of the subsequent electrical property test.
6、利用电学装置测试晶片电学性质,并对测试结果进行分析6. Use electrical devices to test the electrical properties of the chip, and analyze the test results
欧姆接触金属电极制作好后,用探针台和霍尔测试设备分别测试了样品的电流、电压特性,电阻率,空穴浓度及迁移率等电学性质。图2为经过不同电压电化学处理之后p型AlGaN样品的IV曲线图,从图中可以看出,4个样品的IV曲线都呈现为线性关系,说明4个样品都形成了良好的欧姆接触,并且可明显看出,经过电化学激活处理样品的电流都要大于未经处理的参考样品,且电化学处理外加偏压越大,电流值也就越高。图3为4个p型AlGaN样品的电阻率大小,与IV曲线的变化趋势一致,经过电化学激活处理之后,样品的电阻率明显降低,且电化学处理所加电压越大,获得的电阻率值越低。与参考样品相比,经过2V、4V和6V电压下电化学激活处理后,样品电阻率分别下降了69.7%、84.9%和87.9%。参考样品由于电阻率过高而无法得到确切的空穴浓度和迁移率,但经过电化学处理之后,空穴浓度都得到了不同程度的提升,在2V、4V和6V的外加偏压处理下,空穴浓度分别提升至4.26×1017、6.81×1017和6.61×1017cm-3,迁移率分别为1.07、1.10和1.54m2·V-1·s-1。IV曲线、电阻率、空穴浓度及迁移率的测试结果都强有力地证明了三电极恒电位电化学激活处理可明显改善p型AlGaN样品的导电性能。不同电压电化学处理样品的常温霍尔测试结果参见表2。After the ohmic contact metal electrode was fabricated, the electrical properties of the sample, such as current and voltage characteristics, resistivity, hole concentration and mobility, were tested with a probe station and Hall test equipment. Figure 2 is the IV curves of p-type AlGaN samples after electrochemical treatment at different voltages. It can be seen from the figure that the IV curves of the four samples all present a linear relationship, indicating that the four samples have formed good ohmic contacts. And it can be clearly seen that the current of the sample treated with electrochemical activation is greater than that of the untreated reference sample, and the greater the bias voltage applied to the electrochemical treatment, the higher the current value. Figure 3 shows the resistivity of the four p-type AlGaN samples, which is consistent with the change trend of the IV curve. After the electrochemical activation treatment, the resistivity of the sample is significantly reduced, and the greater the applied voltage of the electrochemical treatment, the obtained resistivity The lower the value. Compared with the reference sample, the resistivity of the sample decreased by 69.7%, 84.9% and 87.9% after electrochemical activation at 2V, 4V and 6V, respectively. The exact hole concentration and mobility of the reference sample cannot be obtained due to the high resistivity, but after electrochemical treatment, the hole concentration has been improved to varying degrees. Under the applied bias treatment of 2V, 4V and 6V, The hole concentration increased to 4.26×10 17 , 6.81×10 17 and 6.61×10 17 cm -3 , and the mobility was 1.07, 1.10 and 1.54m 2 ·V -1 ·s -1 , respectively. The test results of IV curve, resistivity, hole concentration and mobility all strongly prove that the three-electrode constant potential electrochemical activation treatment can significantly improve the conductivity of p-type AlGaN samples. See Table 2 for room temperature Hall test results of electrochemically treated samples at different voltages.
表2Table 2
7、三电极恒电位电化学处理激活提升氮化物半导体p型导电性的原理解释7. Explanation of the principle of three-electrode potentiostatic electrochemical treatment activation to enhance the p-type conductivity of nitride semiconductors
使用金属有机物气相外延等方法生长III族氮化物半导体材料时会不可避免地引入H原子杂质,而H原子会与p型掺杂原子如Mg结合形成络合物,因此钝化掉p型掺杂原子的受主活性。传统上使用高温退火工艺打断Mg-H键连,除去H,恢复p型掺杂原子的活性,如下所示:When growing III-nitride semiconductor materials by metal-organic vapor phase epitaxy and other methods, H atom impurities will inevitably be introduced, and H atoms will combine with p-type dopant atoms such as Mg to form complexes, thus passivating p-type doping Atom acceptor activity. Traditionally, a high-temperature annealing process is used to break the Mg-H bond, remove H, and restore the activity of p-type dopant atoms, as follows:
在三电极恒电位电化学激活过程中,外加电压起到和高温相同的作用,Mg-H键连在外加电压的作用下断开,Mg受主活性被激活,并产生H+离子。在工作电极和辅助电极之间电势梯度的作用下,H+离子扩散至材料表明,并且与电解液中的H2O、Cl-、OH-及H+等分子和离子相结合,最终脱离p型氮化物材料,如下所示:In the three-electrode constant potential electrochemical activation process, the applied voltage plays the same role as high temperature, the Mg-H bond is broken under the applied voltage, the Mg acceptor activity is activated, and H + ions are generated. Under the action of the potential gradient between the working electrode and the auxiliary electrode, H + ions diffuse to the surface of the material, and combine with molecules and ions such as H 2 O, Cl - , OH - and H + in the electrolyte, and finally detach from p type nitride materials, as follows:
H++H2O→H3O+ H + +H 2 O→H 3 O +
H++Cl-→HClH + +Cl - →HCl
H++OH-→H2OH + +OH - → H 2 O
H++H++2e→H2 H + +H + +2e → H 2
图4为p型GaN材料表面H+离子与HCl溶液中Cl-离子结合并脱离GaN的过程示意图,整个过程中原子位置的变化由VASP第一性原理计算所得到。可以看出,Cl-离子首先在电荷的相互作用下靠近H+,并与H+离子结合形成HCl,最终将H+拖离开样品表面。Figure 4 is a schematic diagram of the process of H + ions on the surface of p-type GaN materials combining with Cl - ions in HCl solution and detaching from GaN. The changes of atomic positions during the whole process are obtained by VASP first-principle calculations. It can be seen that Cl - ions first approach H + under the interaction of charges, and combine with H + ions to form HCl, and finally drag H + away from the sample surface.
图5中所示的SIMS元素分布表明三电极恒电位电化学处理确实能够有效地降低p型AlGaN样品中的H原子浓度。在靠近样品表面的p型GaN接触层中,所加电压为4V时H原子浓度降低最多,电化学除H效果最好,在p型AlGaN层中,电压为6V时H原子浓度最低,除H效果最好,这表明电化学激活处理对于不同Al组分的AlGaN的效果有所区别。但是总体而言,SIMS元素分析表明三电极恒电位电化学处理可有效打断p型杂质与H原子的键连,并将H从样品中移除,降低样品中的H原子浓度,进而激活p型杂质的受主活性,提高空穴浓度,最终改善氮化物半导体材料的p型导电性。The SIMS element distribution shown in Fig. 5 shows that the three-electrode potentiostatic electrochemical treatment can indeed effectively reduce the concentration of H atoms in the p-type AlGaN samples. In the p-type GaN contact layer close to the sample surface, the concentration of H atoms decreases the most when the applied voltage is 4V, and the effect of electrochemical H removal is the best. In the p-type AlGaN layer, the concentration of H atoms is the lowest when the voltage is 6V. The effect is the best, which shows that the electrochemical activation treatment has a different effect on AlGaN with different Al compositions. But in general, SIMS elemental analysis shows that the three-electrode constant potential electrochemical treatment can effectively break the bond between p-type impurities and H atoms, remove H from the sample, reduce the concentration of H atoms in the sample, and activate p The acceptor activity of the type impurity increases the hole concentration, and finally improves the p-type conductivity of the nitride semiconductor material.
Claims (7)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810298037.5A CN108519411A (en) | 2018-03-30 | 2018-03-30 | A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity |
CN202010864102.3A CN112098481B (en) | 2018-03-30 | 2018-03-30 | Device for dehydrogenation activation of nitride semiconductor material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810298037.5A CN108519411A (en) | 2018-03-30 | 2018-03-30 | A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010864102.3A Division CN112098481B (en) | 2018-03-30 | 2018-03-30 | Device for dehydrogenation activation of nitride semiconductor material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108519411A true CN108519411A (en) | 2018-09-11 |
Family
ID=63431453
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810298037.5A Pending CN108519411A (en) | 2018-03-30 | 2018-03-30 | A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity |
CN202010864102.3A Active CN112098481B (en) | 2018-03-30 | 2018-03-30 | Device for dehydrogenation activation of nitride semiconductor material |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010864102.3A Active CN112098481B (en) | 2018-03-30 | 2018-03-30 | Device for dehydrogenation activation of nitride semiconductor material |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN108519411A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118156122A (en) * | 2024-05-11 | 2024-06-07 | 苏州立琻半导体有限公司 | Electrochemical processing equipment for nitride semiconductor and processing technology for wafer doping |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114628562B (en) * | 2022-03-11 | 2025-02-11 | 安徽格恩半导体有限公司 | A semiconductor light emitting element having a hydrogen evolution layer |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070029558A1 (en) * | 2005-08-03 | 2007-02-08 | Kyocera Corporation | Method for manufacturing p-type gallium nitride compound semiconductor, method for activating p-type impurity contained in gallium nitride compound semiconductor, and apparatus for activating p-type impurity contained in gallium nitride compound semiconductor |
US20090239344A1 (en) * | 2008-03-24 | 2009-09-24 | Samsung Electronics Co., Ltd. | Methods of Forming Field Effect Transistors Having Silicided Source/Drain Contacts with Low Contact Resistance |
CN102031484A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院半导体研究所 | Method for improving activation efficiency of magnesium-doped nitrides under catalytic dehydrogenation of metals |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4694395B2 (en) * | 2006-03-22 | 2011-06-08 | 日本オプネクスト株式会社 | Nitride semiconductor light emitting device and manufacturing method thereof |
CN102089864A (en) * | 2008-05-12 | 2011-06-08 | 加利福尼亚大学董事会 | Photoelectrochemical etching of P-type semiconductor heterostructures |
EP3923352A1 (en) * | 2010-01-27 | 2021-12-15 | Yale University, Inc. | Conductivity based selective etch for gan devices and applications thereof |
JP6047995B2 (en) * | 2012-08-22 | 2016-12-21 | 住友電気工業株式会社 | Method of manufacturing group III nitride semiconductor, method of manufacturing semiconductor element, group III nitride semiconductor device, method of performing heat treatment |
JP2017516289A (en) * | 2014-02-10 | 2017-06-15 | レンセラール ポリテクニック インスティチュート | Selective electrochemical etching of semiconductors |
-
2018
- 2018-03-30 CN CN201810298037.5A patent/CN108519411A/en active Pending
- 2018-03-30 CN CN202010864102.3A patent/CN112098481B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070029558A1 (en) * | 2005-08-03 | 2007-02-08 | Kyocera Corporation | Method for manufacturing p-type gallium nitride compound semiconductor, method for activating p-type impurity contained in gallium nitride compound semiconductor, and apparatus for activating p-type impurity contained in gallium nitride compound semiconductor |
US20090239344A1 (en) * | 2008-03-24 | 2009-09-24 | Samsung Electronics Co., Ltd. | Methods of Forming Field Effect Transistors Having Silicided Source/Drain Contacts with Low Contact Resistance |
CN102031484A (en) * | 2010-10-13 | 2011-04-27 | 中国科学院半导体研究所 | Method for improving activation efficiency of magnesium-doped nitrides under catalytic dehydrogenation of metals |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118156122A (en) * | 2024-05-11 | 2024-06-07 | 苏州立琻半导体有限公司 | Electrochemical processing equipment for nitride semiconductor and processing technology for wafer doping |
CN118156122B (en) * | 2024-05-11 | 2024-08-20 | 苏州立琻半导体有限公司 | Electrochemical processing equipment for nitride semiconductor and processing technology for wafer doping |
Also Published As
Publication number | Publication date |
---|---|
CN112098481B (en) | 2021-08-27 |
CN112098481A (en) | 2020-12-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Fujii et al. | Hydrogen gas generation by splitting aqueous water using n-type GaN photoelectrode with anodic oxidation | |
Ebaid et al. | Water splitting to hydrogen over epitaxially grown InGaN nanowires on a metallic titanium/silicon template: reduced interfacial transfer resistance and improved stability to hydrogen | |
Young et al. | Remarkable stability of unmodified GaAs photocathodes during hydrogen evolution in acidic electrolyte | |
Echendu et al. | Characterization of n-type and p-type ZnS thin layers grown by an electrochemical method | |
Laflere et al. | On the differential capacitance of the n-and p-type gallium arsenide electrode | |
Deutsch et al. | Photoelectrochemical characterization and durability analysis of GaInPN epilayers | |
Yamamoto et al. | Anodic Dissolution of N‐Type Gallium Arsenide under Illumination | |
CN108519411A (en) | A method of dehydrogenation and activation of nitride semiconductor materials to improve p-type conductivity | |
Zhang et al. | Metal-assisted photochemical etching of gallium nitride using electrodeposited noble metal nanoparticles as catalysts | |
Fujii et al. | Hydrogen generation from aqueous water using n‐GaN by photoassisted electrolysis | |
CN106374000B (en) | The preparation method and applications of black silicon photocathode | |
Zhao et al. | Electrochemical deposition of copper on single-crystal gallium nitride (0001) electrode: nucleation and growth mechanism | |
Jayathileke et al. | Electrodeposition of p-type, n-type and pn Homojunction Cuprous Oxide Thin Films | |
Lebedev et al. | Charge transport at the interface of n-GaAs (100) with an aqueous HCl solution: Electrochemical impedance spectroscopy study | |
De Mierry et al. | Defects Induced in p‐Type Silicon by Photocathodic Charging of Hydrogen | |
Fujii et al. | Photoelectrochemical properties of nonpolar and semipolar GaN | |
CN101840964B (en) | Preparation method of low-resistance p-GaN ohmic contact electrode | |
Shiraz et al. | The effect of a porous layer on IV characterization of a polysilicon pn junction | |
Kang et al. | Low-temperature synthesis of GaN film from aqueous solution by electrodeposition | |
Janousek et al. | Hg0. 70Cd0. 30Te anodic oxidation | |
Asil et al. | Temperature dependent current-voltage characteristics of electrodeposited p-ZnO/n-Si heterojunction | |
Goryachev et al. | Electrolytic fabrication of porous silicon with the use of internal current source | |
KR101171817B1 (en) | METHOD FOR MANUFACTURING P-TYPE GaN-BASED COMPOUND SEMICONDUCTOR, METHOD FOR ACTVATING P-TYPE DOPANT CONTAINED IN GaN-BASED COMPOUND SEMICONDUCTOR, GaN-BASED COMPOUND SEMICONDUCTOR DEVICE, AND GaN-BASED COMPOUND SEMICONDUCTOR LIGHT-EMITTING DEVICE | |
Shin et al. | All-Solution Processedn n-ZnO Nanorods/i-CdS/p-Cu2O Diodes Prepared Using Diluted Solution Precursors | |
Wang et al. | Characterization of electro-deposited CuO as a low-cost material for high-efficiency solar cells |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180911 |