CN112098481B - Device for dehydrogenation activation of nitride semiconductor material - Google Patents
Device for dehydrogenation activation of nitride semiconductor material Download PDFInfo
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- CN112098481B CN112098481B CN202010864102.3A CN202010864102A CN112098481B CN 112098481 B CN112098481 B CN 112098481B CN 202010864102 A CN202010864102 A CN 202010864102A CN 112098481 B CN112098481 B CN 112098481B
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- G—PHYSICS
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- 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
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Abstract
The invention relates to the technical field of p-type conductivity of nitride semiconductor materials, in particular to a device and a method for dehydrogenation activation of nitride semiconductor materials. The invention adopts a constant potential electrochemical device, the acceptor activity of the p-type impurity is activated by breaking the bond between the p-type impurity and the H atom and removing the H from the sample, and the bond between the H atom and the p-type impurity can be effectively broken and separated from the sample under the combined action of the applied voltage and the electrolyte ions, so that the p-type impurity is quickly activated, the hole concentration is improved, and the conductive property of the p-type material can be greatly improved. The method has the advantages of simple device, simple operation and normal-temperature work, can prepare the p-type nitride semiconductor material with good conductive property, can perform post-treatment on the wafer with the complete device structure, and has wide application prospect and development potential in the photoelectronic fields of visible light, ultraviolet, deep ultraviolet LED, LD, detectors and the like.
Description
Technical Field
The invention relates to the technical field of p-type conductivity of nitride semiconductor materials, in particular to a device and a method for dehydrogenation activation of nitride semiconductor materials.
Background
The nitride semiconductor material has the unique advantages of wide direct band gap adjustable range, good structural stability, high critical breakdown voltage and the like, and becomes a material basis for preparing short-wavelength high-brightness light emitting diodes, high-power lasers, high-sensitivity photodetectors and high-temperature high-power electronic devices. Visible blue-green light, ultraviolet and deep ultraviolet optoelectronic devices have been greatly developed in the past decade under the continuous and concerted efforts of numerous researchers and industries. However, compared with GaN-based visible light and near ultraviolet photoelectronic devices, AlGaN ultraviolet photoelectronic devices have generally low working efficiency, and the key reasons are the intrinsic characteristics of AlGaN material systems and the difficult-to-overcome scientific problems in device processes, including low epitaxial crystal quality of AlGaN materials with high Al content, strong optical anisotropy, spontaneous polarization and piezoelectric polarization of AlGaN materials with high Al content, difficulty in p-type doping and activation, and the like.
Doping plays a key role in the fabrication of semiconductor devices as one of the most important means for controlling the conductivity of semiconductors. At present, the n-type doping efficiency of the III group nitride semiconductor material is higher, higher electron concentration can be provided, and the use requirements of various photoelectronic devices are met. Compared with n-type doping, the p-type doping efficiency of the existing III-group nitride semiconductor material is generally low, particularly in AlGaN materials with high Al components, p-type impurities are easy to form deep energy levels, the acceptor activation energy is high, the activation efficiency of the impurities is low, so that the conductivity of the p-type AlGaN material is generally at a low level and the use requirements of various photoelectronic devices cannot be met. And H atoms introduced in the growth process of the material are easy to combine with p-type impurities to form a complex, so that the acceptor activity of the p-type impurities is passivated, the hole concentration of the material is reduced, and the p-type conductivity of the AlGaN material is further reduced.
In order to improve the conductivity of p-type nitride materials, researchers have proposed a number of methods including polarization-induced doping, superlattice doping, delta doping, and acceptor-donor co-doping, among others. Aiming at the problem of acceptor activity of H atom passivation p-type impurities, in 1989, an Amano research group in Japan breaks the bond between the Mg and the H of the p-type impurities through a low-energy electron beam irradiation process, removes the H, recovers the acceptor activity of the Mg impurities, and obtains a p-type GaN sample for the first time. Subsequently, Nakamura research group of Japan, 1992, found that thermal annealing in a nitrogen atmosphere can exert the same H-removing effect as low-energy electron beam irradiation, and that a highly conductive p-type GaN material can be obtained more conveniently. Compared with GaN, AlGaN materials are more difficult to p-type activate and require higher annealing temperatures. Although annealing is currently the most common activation method for p-type AlGaN materials, it requires a high temperature of 800 ℃ or higher, and thus it is easy to form defect compensation centers such as nitrogen vacancies during activation, and reduces the hole concentration, which makes it difficult to obtain an optimal activation effect, and limits further improvement of conductivity of p-type AlGaN materials.
Disclosure of Invention
In order to solve the problem of difficult dehydrogenation of the nitride semiconductor material, the invention provides a device for dehydrogenation activation of the nitride semiconductor material, which comprises an electrolyte container, wherein the bottom of the electrolyte container is provided with an opening, and a p-type doped nitride semiconductor wafer is placed below the opening;
one end of the auxiliary electrode and one end of the reference electrode are arranged in the electrolyte container and can be in contact with the electrolyte in the electrolyte container, and the other end of the auxiliary electrode and the other end of the reference electrode penetrate through the side wall of the electrolyte container and are connected with an external testing device;
and the probe or the lead is electrically connected with the p-type doped nitride semiconductor wafer, wherein the p-type doped nitride semiconductor wafer is used as a working electrode.
On the basis of the technical scheme, further, the solution of the electrolyte container is one of HCl, HF, HBr and HI solution; of course, the device is also suitable for NaOH, KOH, Ca (OH)2As an electrolyte. Preparing electrolyte with different concentrations according to different components, structures, thicknesses and other experimental conditions of the p-type semiconductor chip; if the concentration of the electrolyte is too low, the efficiency of H is not high, and the concentration is too high, so that the surface of the wafer is easily corroded by the solution under the combined action of the applied voltage.
On the basis of the above technical solution, further, a metal electrode is disposed on the p-type doped nitride semiconductor wafer, or an indium contact metal is disposed on the p-type doped nitride semiconductor wafer, and the indium contact metal is in electrical contact with the probe or the wire.
When an external probe or a lead is in contact with a p-type wafer serving as a working electrode, in order to reduce the influence of a contact potential barrier, a metal electrode can be manufactured on the surface of the wafer, or indium is used as a contact metal to improve the electrical contact.
On the basis of the technical scheme, the electrolyte container is further made of a Teflon material or a quartz material.
On the basis of the technical scheme, an O-shaped sealing ring is further arranged between the opening and the p-type doped nitride semiconductor wafer;
the auxiliary electrode and the other end of the auxiliary electrode penetrate through the side wall of the electrolyte container and are sealed;
the auxiliary electrode and the reference electrode are arranged in parallel with the p-type doped nitride semiconductor wafer; the whole uniformity of the electrochemical treatment can be improved as much as possible by parallel arrangement.
On the basis of the technical scheme, the auxiliary electrode comprises, but is not limited to, an inert conductive material in which platinum, lead, copper, titanium, tin and graphite are insoluble in an electrolyte, and the shape of the auxiliary electrode is flaky and has a large surface area, so that externally applied polarization mainly acts on the working electrode; the reference electrode includes, and is not limited to, a Saturated Calomel Electrode (SCE), an Ag/AgCl electrode, and a standard hydrogen electrode (SHE or NHE), allowing for good potential stability and reproducibility of the reference electrode.
On the basis of the technical scheme, the p-type doped nitride semiconductor wafer has a single-layer, multi-layer, superlattice and component gradient structure and comprises a p-type layer complete LED, LD and detector.
The invention also provides a method for dehydrogenation activation of the nitride semiconductor material, which comprises the following steps:
step a, placing a p-type doped nitride semiconductor in an electrochemical treatment device, using the p-type doped nitride semiconductor as a working electrode, arranging an auxiliary electrode and a reference electrode, and forming an electrochemical three-electrode system with the working electrode;
b, selecting one of HCl, HF, HBr and HI solution as hydrogen removal electrolyte, adding the hydrogen removal electrolyte into the electrochemical treatment device, and submerging the three electrodes;
and c, applying direct current bias between the working electrode and the auxiliary electrode, wherein the bias is 2-10V and the duration is 5-20 min, and then the dehydrogenation activation of the nitride semiconductor material is completed.
Bias and processing time are two key parameters of the experiment, too low bias and too short processing time can not achieve the best activation effect, and too high bias and too long processing time can cause certain corrosion and damage to the surface of the wafer.
On the basis of the above technical solution, further, the elements of the p-type doped nitride semiconductor include at least two of Mg, Zn, Cd, Be, Ca, and Ba.
On the basis of the technical scheme, further, after the dehydrogenation activation of the nitride semiconductor material is completed in the step c, the p-type doped nitride semiconductor wafer is taken out, deionized water ultrasonic cleaning is carried out, and the electrical property of the wafer can be tested by utilizing an electrical device.
The invention provides a device for dehydrogenation activation of nitride semiconductor materials, which is simple in device, simple and convenient to operate, capable of working at normal temperature, free of high-temperature annealing and free of additional defects, can be used for preparing p-type nitride semiconductor materials with good conductivity, can be used for GaN and AlGaN materials, can be used for post-processing of prepared wafers with complete device structures, is suitable for large-scale industrial popularization, and has wide application prospect and development potential in the photoelectron fields of ultraviolet, deep ultraviolet LEDs, LDs, detectors and the like.
Specifically, with this patent, whether the sample being processed is a pure p-type structure or a complete device wafer containing 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 such as an LED, an LD, a detector, etc. with a complex structure, due to the existence of complex structures such as an n-type layer, an active layer, etc., if the entire sample is in contact with the electrolyte, the applied voltage and the current of the loop may be unstable, resulting in a poor activation effect of the final p-type layer. Only the surface of the p-type layer is contacted with the electrolyte, so that the influence of complex structures such as an n-type layer, an active layer and the like on potential and current can be eliminated, and the optimal activation effect of the p-type layer is ensured.
The invention also provides a novel activation and promotion method for p-type conductivity of the nitride semiconductor material, which mainly adopts constant potential electrochemical treatment to break the bond between the p-type impurity and H, removes H from a sample by utilizing potential gradient and ion activity in a dehydrogenation solvent, activates the acceptor activity of the p-type impurity, greatly reduces the resistivity of the sample, improves the hole concentration and improves the p-type conductivity of the nitride semiconductor material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an apparatus for dehydrogenation activation of nitride semiconductor material according to the present invention;
FIG. 2 is a graph of the IV curve of a p-type AlGaN sample after different voltage electrochemical treatments;
FIG. 3 shows the resistivity levels of p-type AlGaN samples after different voltage electrochemical treatments;
FIG. 4 shows a p-type GaN surface H+Ion and Cl in hydrochloric acid solution-Schematic representation of the process of ion binding and dissociation from the sample;
fig. 5 is a SIMS elemental profile of a p-type AlGaN sample after different voltage electrochemical treatments.
Reference numerals:
10 electrolyte container 11 open 20 p-type doped nitride semiconductor wafer
31 auxiliary electrode 32 reference electrode 21 probe or lead
22 contact metal 23O-shaped sealing ring
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The invention provides a device for dehydrogenation activation of nitride semiconductor materials, which comprises an electrolyte container 10, wherein an opening 11 is formed in the bottom of the electrolyte container 10, and a p-type doped nitride semiconductor wafer 20 is placed below the opening 11;
the test device also comprises an auxiliary electrode 31 and a reference electrode 32, wherein one end of the auxiliary electrode 31 and one end of the reference electrode 32 are arranged in the electrolyte container 10 and can be contacted with the electrolyte in the electrolyte container 10, and the other end of the auxiliary electrode 31 and the other end of the reference electrode 32 penetrate through the side wall of the electrolyte container 10 and are connected with an external test device;
and a probe or wire 21 electrically connected to the p-type doped nitride semiconductor wafer 20, the p-type doped nitride semiconductor wafer 20 serving as a working electrode.
Preferably, the solution of the electrolyte container 10 is one of HCl, HF, HBr, HI solution; of course, the device is also suitable for NaOH, KOH, Ca (OH)2As an electrolyte. Preparing electrolyte with different concentrations according to different components, structures, thicknesses and other experimental conditions of the p-type semiconductor chip; if the concentration of the electrolyte is too low, the efficiency of H is not high, and the concentration is too high, so that the surface of the wafer is easily corroded by the solution under the combined action of the applied voltage.
Preferably, a metal electrode is provided on the p-type doped nitride semiconductor wafer 20, or an indium contact metal 22 is provided, and the indium contact metal is in electrical contact with the probe or the wire.
Specifically, when the external probe or wire 21 is brought into contact with the p-type doped nitride semiconductor wafer 20 as the working electrode, a metal electrode may be formed on the wafer surface or indium may be used as the contact metal 22 to improve the electrical contact thereof in order to reduce the influence of the contact barrier.
Preferably, the electrolyte container 10 is made of teflon material or quartz material.
Preferably, an O-ring seal 23 is provided between the opening 11 and the p-type doped nitride semiconductor wafer 20;
the auxiliary electrode 31 and the other end penetrate through the side wall of the electrolyte container 10 and are sealed;
the auxiliary electrode 31 and the reference electrode 32 are disposed in parallel with the p-type doped nitride semiconductor wafer 20; by placing them in parallel, the overall uniformity of the electrochemical treatment can be improved as much as possible.
Further, the auxiliary electrode 31 includes, but is not limited to, an inert conductive material in which platinum, lead, copper, titanium, tin and graphite are insoluble in the electrolyte, and is shaped like a sheet having a large surface area so that externally applied polarization mainly acts on the working electrode; the reference electrode 32 includes, and is not limited to, a Saturated Calomel Electrode (SCE), an Ag/AgCl electrode, and a standard hydrogen electrode (SHE or NHE), allowing for good potential stability and reproducibility of the reference electrode.
Further, the p-type doped nitride semiconductor wafer 20 has a single-layer, multi-layer, superlattice and composition-graded structure, including a p-type layer of complete LED, LD, and detector.
The present invention also provides the following embodiments:
1. electrochemical three-electrode experimental device for activating and improving p-type conductivity of nitride semiconductor material
Firstly, an electrochemical three-electrode experimental device for activating and promoting p-type conductivity of nitride semiconductor materials is designed and manufactured. As shown in fig. 1, the electrolyte container 10 of the electrochemical three-electrode device used in this embodiment is made of teflon, the bottom of the container is provided with an opening 11 for the working electrode to contact with the electrolyte, the opening is sealed by a fluorine rubber O-ring, and the working electrode and the container can be clamped by a buckle. The auxiliary electrode 31 is a platinum sheet (Pt plate) and the reference electrode 32 is a Saturated Calomel Electrode (SCE), which are fixed and sealed to the side wall of the container, respectively. The three electrodes are placed in parallel to ensure the overall uniformity of the electrochemical treatment as much as possible. The working electrode is connected to an external power source by a probe with a telescopic spring and a lead 21, and the electrical contact between the probe and the p-type working electrode is improved by an indium contact metal 22.
2. After the electrochemical three-electrode experimental device is manufactured, the preparation stage of the experiment is started
1) The p-type AlGaN wafer processed in this example was epitaxially grown by MOCVD and had an average composition of about 40%. The wafer is sealed to the bottom of the container to be used as a working electrode, and the wafer and the container are clamped by a buckle. After the snap-fit, the probe with the pogo spring, the indium contact metal and the p-type doped nitride semiconductor wafer 20 form good electrical contact.
2) And connecting the three electrodes with an external direct current power supply by using a lead to form the electrochemical three-electrode experimental system.
3) A HCl solution with a concentration of 1.0M was prepared as the dehydrogenation electrolyte and added to the container until the three electrodes were completely submerged.
3. Entering the experimental reaction stage to remove H activation and increase the p-type conductivity of the wafer
After the experimental preparation work is finished, applying a direct current bias voltage between the working electrode and the auxiliary electrode by using an external power supply, entering an experimental reaction stage, starting to remove H activation and improve the p-type conductivity of the AlGaN wafer for a period of time. In this example, p-type AlGaN wafers were subjected to electrochemical activation under different conditions, wherein three samples were biased at 2V, 4V, and 6V for 5 minutes. Another sample was not electrochemically treated and was used as a reference sample to examine the effects of electrochemical treatment. The experimental conditions for each sample are shown in table 1.
TABLE 1 three-electrode potentiostatic electrochemical treatment experimental conditions
| Sample (I) | | # | 1 | #2 | #3 |
| Voltage (V) | 0 | 2 | 4 | 6 | |
| Duration (min) | 0 | 5 | 5 | 5 |
4. After the activation process, the wafer is taken out and cleaned
And after the electrochemical activation treatment is finished, pouring out the electrolyte, taking down the p-type AlGaN wafer, soaking the wafer in deionized water, cleaning the wafer for ten minutes by using ultrasonic waves, and then placing the wafer on a baking table for drying so as to remove the electrolyte and the deionized water which are remained on the surface of the sample.
5. Ohmic contact metal electrode fabrication
After the wafer is cleaned, 40nm of Ni metal is plated on the sample to serve as an electrode by using a magnetron sputtering method, and after thermal annealing for 15 minutes at 480 ℃ in a nitrogen atmosphere, good ohmic contact is formed between the Ni metal and the p-type AlGaN sample, so that the reliability and stability of subsequent electrical property tests are guaranteed.
6. Testing the electrical properties of the wafer by using an electrical device, and analyzing the test results
After the ohmic contact metal electrode is manufactured, the probe station and the Hall test equipment are used for respectively testing the current and voltage characteristics, the resistivity, the hole concentration, the mobility and other electrical properties of the sample.
Fig. 2 is a graph of the IV curves of p-type AlGaN samples after electrochemical treatment at different voltages, and it can be seen from the graph that the IV curves of the four samples all show a linear relationship, which indicates that the four samples all form good ohmic contact, and it is obvious that the current of the sample after electrochemical activation treatment is greater than that of the untreated reference sample, and the larger the electrochemical treatment applied bias is, the higher the current value is.
Fig. 3 shows the resistivity of four p-type AlGaN samples, which is consistent with the variation trend of the IV curve, and after the electrochemical activation treatment, the resistivity of the sample is significantly reduced, and the higher the voltage applied by the electrochemical treatment, the lower the obtained resistivity value. Compared with the reference sample, the resistivity of the sample is reduced by 69.7%, 84.9% and 87.9% after electrochemical activation treatment at voltages of 2V, 4V and 6V respectively. The reference sample cannot obtain exact hole concentration and mobility due to the fact that the resistivity is too high, but the hole concentration is improved to different degrees after electrochemical treatment, and the hole concentration is improved to 4.26 multiplied by 10 under the external bias treatment of 2V, 4V and 6V respectively17、6.81×1017And 6.61X 1017cm-3The mobility is 1.07, 1.10 and 1.54m respectively2V-1·s-1. The test results of IV curve, resistivity, hole concentration and mobility strongly prove that the conductivity of the p-type AlGaN sample can be obviously improved by the three-electrode constant potential electrochemical activation treatment.
TABLE 2 Normal temperature Hall test results for different voltage electrochemically treated samples
| Sample (I) | | # | 1 | #2 | #3 |
| Concentration of holes (cm)-3) | * | 4.26×1017 | 6.81×1017 | 6.61×1017 | |
| Mobility (cm)2V-1s-1) | * | 1.07 | 1.10 | 1.54 |
7. Principle explanation for activating and improving p-type conductivity of nitride semiconductor by three-electrode constant potential electrochemical treatment
When a group III nitride semiconductor material is grown by a method such as metal organic vapor phase epitaxy, H atom impurities are inevitably introduced, and the H atoms combine with p-type dopant atoms such as Mg to form a complex, thereby inactivating the acceptor activity of the p-type dopant atoms. High temperature annealing processes have traditionally been used to break Mg-H bonds, remove H, and restore the activity of p-type dopant atoms as follows:
in the process of three-electrode constant potential electrochemical activation, the applied voltage has the same effect as high temperature, Mg-H bond is broken under the action of the applied voltage, Mg acceptor activity is activated, and H is generated+Ions. Under the action of the potential gradient between the working electrode and the auxiliary electrode, H+Ion diffusion to the surface of the material and with H in the electrolyte2O、Cl-OH-and H+Molecules and ions are combined to finally separate from the p-type nitride material, as shown below:
H++H2O→H3O+
H++Cl-→HCl
H++OH-→H2O
H++H++2e→H2
FIG. 4 shows a p-type GaN material surface H+Ion and Cl in HCl solution-The process of ion combination and separation from GaN is shown schematically, and the change of atomic position in the whole process is calculated by VASP first principle. As can be seen, Cl-Ions first approach H under charge interaction+And is combined with H+The ions combine to form HCl, which eventually reacts with H+Away from the sample surface.
The SIMS elemental distribution shown in fig. 5 indicates that the three-electrode potentiostatic electrochemical treatment is indeed effective in reducing the H atom concentration in p-type AlGaN samples. In the p-type GaN contact layer close to the surface of the sample, the H atom concentration is reduced most when the applied voltage is 4V, and the electrochemical H removal effect is the best, and in the p-type AlGaN layer, the H atom concentration is the lowest when the applied voltage is 6V, and the electrochemical H removal effect is the best, which shows that the electrochemical activation treatment has different effects on AlGaN with different Al compositions. In general, however, SIMS elemental analysis indicates that three-electrode potentiostatic electrochemical treatment can effectively break down p-type impurities fromBonding of H atoms to each other and formation of H+And removing the nitride semiconductor material from the sample, reducing the concentration of H atoms in the sample, further activating the acceptor activity of the p-type impurity, increasing the concentration of holes and finally improving the p-type conductivity of the nitride semiconductor material.
In the present invention, one selected from HCl, HF, HBr, HI, and a large amount of H present in acid+The ions can be extracted from H in the nitride material+Combine and get electrons at the Pt electrode to generate H2Thereby playing the role of dehydrogenation activation. H originally existing in HCl, HF, HBr and HI of the original electrolyte+Will also take part in the reaction to produce H2Resulting in H in the original electrolyte+Consumption of Cl in the original electrolyte-、F-、Br-、I-The plasma halogen ions accumulate on the surface of the nitride and have a higher concentration under the influence of the electrodes, due to the Cl-、F-、Br-The plasma halide ions have strong electronegativity (next to inert gas elements such as He, Ne, Ar and the like in the periodic table of elements), and can play a role in extracting H in the semiconductor and breaking Mg-H bonds; while, negatively charged Cl-、F-、Br-After the halogen ions are accumulated on the surface of the semiconductor sample, a strong local electric field is generated in the local space on the surface of the sample, and under the action of the strong local electric field, H in the nitride+It also tends to break away from Mg binding quickly and efficiently and diffuse and drift unidirectionally, eventually breaking away from the sample.
Taking HCl as an example, when H+When the sample is separated from the sample and reaches the solution, H is generated due to the strong electronegativity of the halogen ions+Transient with Cl-Combined and substituted with Cl-Ions are dragged away to a diffusion layer in the electrolyte, and then under the action of an external electric field, H+Ion dissociation from Cl-Moving towards the Pt electrode to finally obtain electrons in a loop at the Pt electrode and other H in the solution+Ion binding to form H2Gas, exiting the entire system. In the process, the HCl concentration in the electrolyte is maintained relatively stable.
Additionally, for the preferred embodiments of the present invention:
for electrolyte solubility: taking HCl solution as an example, when the concentration of the solution is 1.0M under an applied voltage of 5V, the hydrogen removal effect and the experimental repetition type are optimal, and the original structure of the wafer is not damaged.
For the magnitude and time of the bias voltage: taking GaN as an example, the activation effect is best when the electrolyte is HCl with a concentration of 1M, the applied voltage is about 4V, and the duration is about 5 minutes. When the Al component of the sample is increased, the applied voltage can be properly increased, for example, the sample with the Al component of about 40 percent has the best activation effect when the applied voltage is about 6V.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. An apparatus for dehydrogenation activation of a nitride semiconductor material, characterized by: the device comprises an electrolyte container, wherein an opening is formed in the bottom of the electrolyte container, and a p-type doped nitride semiconductor wafer is placed below the opening; the surface of the p-type layer of the conductor wafer is positioned in electrolyte, and the electrolyte is only contacted with the surface of the p-type layer in the wafer;
one end of the auxiliary electrode and one end of the reference electrode are arranged in the electrolyte container and can be in contact with the electrolyte in the electrolyte container, and the other ends of the auxiliary electrode and the reference electrode penetrate through the side wall of the electrolyte container and are connected with an external testing device;
the p-type doped nitride semiconductor wafer is provided with a metal electrode or indium contact metal, the indium contact metal is in electrical contact with the probe or the lead, and the probe or the lead is not immersed in electrolyte.
2. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: the solution of the electrolyte container is one of HCl, HF, HBr and HI solution.
3. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: and a metal electrode is arranged on the p-type doped nitride semiconductor wafer, or indium contact metal is arranged on the p-type doped nitride semiconductor wafer, and the indium contact metal is electrically contacted with the probe or the lead.
4. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: the electrolyte container is made of a Teflon material or a quartz material.
5. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: an O-shaped sealing ring is arranged between the opening and the p-type doped nitride semiconductor wafer;
the auxiliary electrode and the other end of the auxiliary electrode penetrate through the side wall of the electrolyte container and are sealed;
the auxiliary electrode and the reference electrode are disposed in parallel with the p-type doped nitride semiconductor wafer.
6. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: the auxiliary electrode includes, but is not limited to, an inert conductive material in which platinum, lead, copper, titanium, tin, and graphite are insoluble in the electrolyte; the reference electrodes include, and are not limited to, saturated calomel electrodes, Ag/AgCl electrodes, and standard hydrogen electrodes.
7. The device for dehydrogenation activation of nitride semiconductor material according to claim 1, characterized in that: the p-type doped nitride semiconductor wafer has a structure of single layer, multiple layers, superlattice and component gradual change, and comprises a complete LED, an LD and a detector of a p-type layer.
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| 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 |
| CN102782818A (en) * | 2010-01-27 | 2012-11-14 | 耶鲁大学 | Conductivity based selective etch for gan devices and applications thereof |
| CN105981131A (en) * | 2014-02-10 | 2016-09-28 | 伦斯勒理工学院 | Selective, electrochemical etching of a semiconductor |
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| US7863201B2 (en) * | 2008-03-24 | 2011-01-04 | 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 |
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| 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 |
| CN102782818A (en) * | 2010-01-27 | 2012-11-14 | 耶鲁大学 | Conductivity based selective etch for gan devices and applications thereof |
| CN105981131A (en) * | 2014-02-10 | 2016-09-28 | 伦斯勒理工学院 | Selective, electrochemical etching of a semiconductor |
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| Application of GaN for photoelectrolysis of water;M V Puzyk 等;《Journal of Physics: Conference Series 643》;20151203;1-5页 * |
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