CN103646868B - Hydro-thermal-vapor etch legal system is for the method for porous silicon - Google Patents
Hydro-thermal-vapor etch legal system is for the method for porous silicon Download PDFInfo
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- CN103646868B CN103646868B CN201310544260.0A CN201310544260A CN103646868B CN 103646868 B CN103646868 B CN 103646868B CN 201310544260 A CN201310544260 A CN 201310544260A CN 103646868 B CN103646868 B CN 103646868B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/0203—Making porous regions on the surface
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02019—Chemical etching
Abstract
The present invention relates to the method for a kind of hydro-thermal-vapor etch legal system for porous silicon, step comprises: process silicon substrate, hydrothermal reaction kettle heating reactant liquor, monocrystalline silicon horse above reactant liquor, reactor is placed in 130 DEG C ~ 190 DEG C temperature baking boxs and reacts, make reactant liquor produce acid vapor, and then the silicon chip of reactant liquor top is produced to corrosion, thereby make porous silicon, by regulating reaction temperature and time, can obtain the porous silicon of stablizing red-emitting. The method is reproducible, and the porous silicon sample of preparation has that light-emitting area is large, stable luminescence, luminous intensity are large and the advantage such as any surface finish.
Description
Technical field
The invention belongs to semiconductor silicon material preparing technical field, be specifically related to a kind of simple, fast and efficient porous siliconPreparation method.
Technical background
Along with the development of information technology, transmission speed, storage capacity, the processing capacity of people to information proposed height moreRequirement. Semi-conducting material particularly silicon-chip technology and photoelectron material and device technology is the basis of information technology, at silicon materialThe integrated circuit growing up on material becomes the key of the information technologies such as development electronic computer, communication and automatic control. ForCan realize integrated-optic device and luminescent device on same silicon chip, namely photoelectron is integrated, development silicon base luminous materialBecome with device the vital task that 21 century scientist need to solve.
Nineteen ninety, Canham further corrodes porous silicon after a few hours, with blue light or UV-irradiation in HF solutionPorous silica material, observes very strong ruddiness in room temperature, this discovery make about the luminescence studies of porous silicon enter one newStage, thus show microelectronics and photoelectron have been integrated in to the possibility on same silicon chip. 1996, the people such as HirschmanIntegrate porous silicon luminescence pipe and silicon planar transistor, made a photoelectron integrated light-emitting array, this is porous silicon lightThe first that electronics is integrated, is an important breakthrough, shows the feasibility that porous silicon photoelectron is integrated.
Existing research shows, the micro-structural of porous and luminosity thereof depend on its preparation technology and condition. At present, systemThe method of standby porous silicon mainly contain electrochemical erosion method, stain etch, photochemical corrosion method, spark-discharge method, pulsed etching method,Etching method, hydrothermal etching etc.
In electrochemical erosion method, adopt platinum filament to make negative electrode, monocrystalline silicon piece is made anode and in HF solution, is carried out electrochemistry corruptionErosion, the relative position insulation effect improper and bubble hydrogen that silicon chip surface forms between anode and negative electrode all can cause electric currentThe spatial variations of density, thus the generation of non-uniform corrosion caused. Its direct result is: cause silicon silk size to have widerDistribute, unfavorable to exploring luminous mechanism; Porous rete is frangible, and the intensity of monoblock sample is low, is difficult to use in the making of device. AnotherAspect, the porous silicon surface that electrochemical erosion method obtains is the interference color of khaki or inhomogeneous form, does not have polishingThe smooth finish surface of monocrystalline silicon, is also provided with obstacle to application.
Stain etch method claims again corrosion, by preparing suitable corrosive liquid, directly monocrystalline silicon piece carry out chemical attack systemStandby porous silicon. Advantage is without bias voltage, and preparation technology is simple, if grow porous silicon in dielectric substrate, this method is more useful;Shortcoming is that the luminous efficiency of goods is lower, and the uniformity of material structure is poor, and experiment repetitive rate is low. In addition, the method exists equallyBecause bubble hydrogen causes the problem of non-uniform corrosion in adhering to of silicon chip surface.
Photochemical corrosion method is under the effect of light, is immersed in crystalline silicon and HF in the HF aqueous solution or ethanolic solution anti-Should. Illumination can produce nonequilibrium carrier in crystalline silicon, and the necessary electronics of reaction and hole are provided, and accelerates surperficial reactionSpeed. In the method, if incident light wavelength is oversize, the energy of photon can be less than the energy gap of silicon and can not produce electricitySon-hole pair; If incident light wavelength is too short, can affect electron-hole pair compared with large absorption because of silicon chip surface againOutput capacity.
Etching method is divided into three kinds of ise, vapor etch and gas etching methods. Ise is the solution containing HF acidBy nozzle, be ejected into bulk silicon substrate surface with certain speed, and then grow porous silicon, but due to relative speedHigh HF drop, in the time clashing into silicon substrate, can be launched other regions, can affect the quality of figure. Vapor etch method is siliconSheet is exposed to the HNO of finite concentration ratio3In the steam of HF mixture. Silicon substrate is placed in the top of acid etch groove, by heatingEtching liquid produces steam, and then forms porous silicon. There is the features such as inexpensive, layer is thin and even with the porous silicon that this method forms, non-Often be adapted at making antireflective coating in solar energy in large area battery and use, its reflectivity is no more than 4%. At present, the method only limits toThe preparation of large area porous silicon layer, application in other respects need further exploitation. Gas etching method is respectively by addingHot NO2、O2With HF acid solution, obtain the mist that temperature is higher, monocrystalline silicon piece is positioned over to the environment of this mistUnder carry out etching, make porous silicon.
That to be seminar of Chinese University of Science and Technology of China corrode by hydro-thermal the one proposing for the preparation of porous silicon to hydrothermal etching is newPorous silicon preparation method. Its concrete preparation process is: the monocrystalline silicon piece cutting is first soaked to 15min with acetone or alcohol, withRemove the organic pollution of surface attachment, more repeatedly rinse well with distilled water; Silicon chip is fixed on to the inner core of high pressure water heating kettleIn; Corrosive liquid (HF, HF+HNO that injection prepares3Solution etc.), heat treatment 1 ~ 3h at 100 ~ 250 DEG C, and naturally coolingTo room temperature; From water heating kettle, take out sample, with distilled water immersion, clean, then under air at room temperature, naturally dry. By controlComposition, concentration and other preparation condition etc. of corrosive liquid processed, can obtain the porous silicon of ruddiness, blue light and ultraviolet light emission. With biographyPorous silicon prepared by system method is compared, and microstructure is similar, stable luminescence, and luminous intensity is high, and mechanical energy is good, the preparation weight of sampleMultiple rate is high, and without post processing. But the problems such as Photoluminescence Intensity of Porous Silicon prepared by hydrothermal etching decay, luminous peak position blue shiftNot yet solve. In order thoroughly to overcome the above problems, seminar of Chinese University of Science and Technology has proposed again employing original position iron passivation hydrothermal etchingPrepare porous silicon.
Summary of the invention
The object of the invention is to propose that one can prepare that light-emitting area is large, stable luminescence, luminous intensity are good, surface lightHydro-thermal-vapor etch legal system of clean, reproducible red emission is for the method for porous silicon.
The technical scheme that technical solution problem of the present invention adopts is: a kind of hydro-thermal-vapor etch legal system is for porous siliconMethod, is characterized in that preparing in the steps below:
Process silicon substrate, use successively acetone and absolute ethyl alcohol ultrasonic cleaning 10min to remove the monocrystalline silicon piece cuttingSurface and oil contaminant, then use the mixed liquor being mixed by the volume ratio of 3:1 by sulfuric acid and hydrogen peroxide to boil 5min, and then use successivelyAcetone and absolute ethyl alcohol ultrasonic cleaning 10min, finally dry for subsequent use with distilled water flushing;
The reactant liquor being mixed by the volume ratio of 23:19:1 by hydrofluoric acid, distilled water and nitric acid is injected into high pressureStill inside liner, compactedness is 70% ~ 90%;
With support by the monocrystalline silicon horse 2mm ~ 8mm above reactant liquor cleaning;
Mounted reactor is put into baking box, and 130 DEG C ~ 190 DEG C temperature ranges, insulation 40 ~ 80min, takes outReactor, rinses and is down to room temperature with running water;
From hydrothermal reaction kettle, take out sample, repeatedly rinse well with distilled water, then nature under air at room temperatureDry.
Hydro-thermal-vapor etch method of the present invention and hydro-thermal method are completely different, and hydro-thermal method is immersed in silicon chip in reactant liquor,And hydro-thermal-vapor etch method by silicon wafer support above reactant liquor liquid level; Hydro-thermal-vapor etch method and traditional vapor etch method are alsoDifference, the reaction temperature of traditional vapor etch method is low, generally below 100 DEG C, needs special equipment, as: thermostat, addHot device, temperature probe and thermoregulator etc., and the reaction temperature of hydro-thermal-vapor etch method is high, at 130 DEG C ~ 190 DEG C, withoutSpecial Equipment, only by hydrothermal reaction kettle and conventional oven.
Mechanism of the present invention and technical characterstic:
Silicon wafer support is more than the liquid level of hydrothermal reaction kettle, and the reactant liquor that heating is mixed by hydrofluoric acid, water and nitric acid, makesReactant liquor produces acid vapor, and then silicon chip is produced to corrosion, thereby makes porous silicon. Silicon substrate be arranged on the above 2mm of liquid level ~8mm, respond temperature and the silicon chip of the volume ratio of fluid component, reactant liquor of the principal element that affects etching effect is exposed to acid vaporIn time.
At a certain temperature, the acid vapor in the above space of hydrothermal reaction kettle liquid level reaches capacity. Along with the rising of temperature,The critical point that the amount of acid vapor can reach capacity and atomization, this makes hydrothermal reaction kettle inwall and surface of silicon be covered with droplet.The size of drop depends on the roughness of surface of silicon and the saturation degree of acid vapor. If silicon substrate is too coarse, acid droplet canCan merge and cause the formation of continuous liquid film. Liquid film can destroy the surface of porous silicon layer or stop hydro-thermal-vapor etch continuouslyThe carrying out of process.
Along with the increase of nitric acid and hydrofluoric acid volume ratio, the content of nitric acid in acid vapor can increase, raising reactant liquorTemperature also can make the content of nitric acid in acid vapor strengthen. Ensure acid vapor stability of flow, must control hydro-thermal reaction wellThe temperature of still, according to the dynamic law of etching process, it is very important keeping acid vapor stability of flow. Work as reacting liquid temperatureLow time, etching speed is also little; Temperature improves, and etching speed can be accelerated; If reacting liquid temperature is too high, acid droplet mayBe merged into large drop and destroy rapidly porous silicon layer. The advantage of hydro-thermal-vapor etch method is that method is simple, cost is low, porous siliconThin and even, any surface finish of layer and luminous intensity are large.
The conventional method of preparing porous silicon is electrochemical erosion method, but the porous silicon that the method makes corrosion is inhomogeneous,Rete mechanical strength is low and frangible, cannot obtain the much higher hole of luminous intensity silicon, also has luminous unstable, luminous efficiency simultaneouslyThe problem such as low. The porous silicon that the present invention adopts hydro-thermal-vapor etch method to make not only has bright and clean surface but also has veryStrong luminescence generated by light, its luminous intensity is approximately 10 times of the prepared porous silicon of electrochemical erosion method, is that vapor etch method is madeFor 8 times of porous silicon. Compared with prior art, hydro-thermal-vapor etch method of the present invention has: simple to operate, cost is low, heavyMultiple rate is high, layer is thin, even, be particularly suitable for preparing large-area porous silicon sample.
Brief description of the drawings
Fig. 1 is that hydro-thermal-vapor etch method is at HF:H2O：HNO3Volume ratio be 23:19:1, compactedness is 80%, silicon chip arrivesReactant liquor liquid level distance is 3mm, and reaction temperature is 140 DEG C, under the condition that the reaction time is 60min, and the porous silicon sample makingStereoscan photograph.
Fig. 2 utilizes the photoluminescence spectrum of porous silicon sample prepared by hydro-thermal-vapor etch method and electrochemical erosion method.
Fig. 3 utilizes the photoluminescence spectrum of hydro-thermal-vapor etch method and the standby porous silicon sample of vapor etch legal system.
Detailed description of the invention
Hydro-thermal-vapor etch legal system, for a method for porous silicon, is characterized in that preparing in the steps below:
1, process silicon substrate: be that 625um, resistivity are the P type of 8 Ω cm～12 Ω cm, single-sided polishing by thicknessSilicon chip is used respectively acetone and absolute ethyl alcohol ultrasonic cleaning 10min, removes dust and the greasy dirt of silicon chip surface, and then uses by sulfuric acidThe mixed liquor mixing by the volume ratio of 3:1 with hydrogen peroxide boils 5min, then uses respectively acetone and absolute ethyl alcohol ultrasonic cleaning10min, finally dries for subsequent use with distilled water flushing.
2, preparation reaction solution: measure hydrofluoric acid (content >=40%) 10.35ml, nitric acid (content 65%-68%) 0.45ml,Distilled water 8.55ml, is mixed with reaction solution 19.5ml, and being poured into cleaned volume is in the reactor inner core of 25ml, fills outThe rate of filling is 70% ~ 90%, and preferred filling rate is 80%;
3, be used for supporting silicon chip with the plastic cross support of a resistance to strong acid and 200 DEG C of high temperature, prevent that silicon chip is directly with anti-Answer liquid contact, above-mentioned support is put into reactor inner core, a top of the trellis exceeds 3mm than reactant liquor liquid level, and silicon chip is lain inOn support; Wherein silicon chip exceeds 2mm ~ 8mm than reactant liquor liquid level and all can;
4, after reactor sealing, put into baking box, be warming up to 140 DEG C, temperature retention time is 60min, after reaction finishes, takes outReactor also rinses and is cooled to room temperature with running water;
5, from hydrothermal reaction kettle, take out sample, repeatedly rinse sample surfaces with distilled water, remove the corrosion of remained on surfaceLiquid, at room temperature dries naturally.
Porous silicon test result prepared by said method
Utilize SEM (FEI-QUANTA200) to characterize the surface topography of porous silicon. At HF:H2O：HNO3Volume ratio be 23:19:1, compactedness is 80%, silicon chip is 3mm to reactant liquor liquid level distance, reaction temperature is 140DEG C, under the condition that the reaction time is 60min, the porous silicon surface making is bright and clean, has obvious loose structure and hole chiVery little more consistent, as shown in Figure 1.
Photoluminescence spectrum and the electrochemical erosion method of the porous silicon sample that hydro-thermal-vapor etch method is prepared under these conditionsPreparation porous silicon sample photoluminescence spectrum more as shown in Figure 2. Electrochemical erosion method is prepared the experiment of porous silicon sampleCondition is: taking thickness as 625um, resistivity is 8 Ω cm～12 Ω cm, the P type silicon chip (back side copper facing) of single-sided polishingFor anode, taking platinum filament as negative electrode, the volume ratio of hydrofluoric acid and absolute ethyl alcohol is 1:1.5, and temperature is room temperature, and electric current is 60mA, anti-Between seasonable, be 43min, platinum filament is 20mm to the distance of silicon chip.
The photoluminescence spectrum of the porous silicon sample that hydro-thermal-vapor etch method is prepared under these conditions and vapor etch legal systemThe photoluminescence spectrum of standby porous silicon sample more as shown in Figure 3. Vapor etch legal system is for the experiment condition of porous silicon sampleBe: thickness is that 625um, resistivity are 8 Ω cm～12 Ω cm, and the P type silicon chip of single-sided polishing, first uses acetone and anhydrous secondThe each ultrasonic cleaning 10min of alcohol, uses H2SO4：H2O2=3:1(volume ratio) mixed liquor boil 5min, with distilled water clean dry. ChoosingThe polytetrafluoro container that is 250ml with volume, configuration HNO3: HF=1:4(volume ratio) solution 180ml, pours into after polytetrafluoro containerWith making support by oneself, the silicon wafer support of handling well is located to liquid level top 2.5cm, cover lid. Polytetrafluoro container is put into freeze-day with constant temperatureIn case, at 40 DEG C of reaction 12min. After reaction finishes, take out distilled water flushing for silicon chip, dry.
Result shows, adopts above-mentioned hydro-thermal-vapor etch legal system for porous silicon sample, and surface is very bright and clean, luminescence generated by lightSpectral intensity (PL spectral intensity) is 10 times that electrochemical erosion method is prepared sample, is 8 times for sample of vapor etch legal system. The methodSimply, cost is low, layer is thin, be applicable to evenly, very much the large-area porous silicon sample of preparation.
Claims (1)
1. hydro-thermal-vapor etch legal system, for a method for porous silicon, is characterized in that preparing in the steps below:
Process silicon substrate, by the monocrystalline silicon piece cutting successively with acetone and absolute ethyl alcohol ultrasonic cleaning 10min to remove surfaceGreasy dirt, then use the mixed liquor being mixed by the volume ratio of 3:1 by sulfuric acid and hydrogen peroxide to boil 5min, and then use acetone successivelyWith absolute ethyl alcohol ultrasonic cleaning 10min, finally dry for subsequent use with distilled water flushing;
The reactant liquor being mixed by the volume ratio of 23:19:1 by hydrofluoric acid, distilled water and nitric acid is injected in autoclaveLining, compactedness is 70% ~ 90%;
With support by the monocrystalline silicon horse 2mm ~ 8mm above reactant liquor cleaning;
Mounted reactor is put into baking box, and 130 DEG C ~ 190 DEG C temperature ranges, insulation 40 ~ 80min, takes out reactionStill, rinses and is down to room temperature with running water;
From hydrothermal reaction kettle, take out sample, repeatedly rinse well with distilled water, then under air at room temperature, naturally dry.
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| CN105417518B (en) * | 2014-09-05 | 2017-07-07 | 中国科学院金属研究所 | Gas phase post processing reforming apparatus and the method for a kind of solid carbonaceous material |
| CN105405930B (en) * | 2015-12-21 | 2017-04-05 | 南昌大学 | A kind of microlayer model etching etching method of solar cell polysilicon chip |
| CN105633422B (en) * | 2016-03-21 | 2018-02-13 | 北京化工大学 | A kind of mass prepares the method that fuel battery negative pole takes off alloy elctro-catalyst with platinum base |
| CN107326444B (en) * | 2017-07-21 | 2019-10-18 | 山东大学 | A kind of method of hydro-thermal corrosion porous-substrates growth self-standing gan monocrystalline |
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| CN111172597B (en) * | 2020-01-21 | 2021-03-26 | 河南理工大学 | Preparation method of luminescent porous silicon |
| CN113773517A (en) * | 2021-10-08 | 2021-12-10 | 上海懿禾嘉朋新材料科技有限公司 | General preparation method of multi-stage porous metal organic framework material |
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