CN1436879A - Prepn of porous liminescent material - Google Patents
Prepn of porous liminescent material Download PDFInfo
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- CN1436879A CN1436879A CN 03115547 CN03115547A CN1436879A CN 1436879 A CN1436879 A CN 1436879A CN 03115547 CN03115547 CN 03115547 CN 03115547 A CN03115547 A CN 03115547A CN 1436879 A CN1436879 A CN 1436879A
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- porous silicon
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Abstract
The present invention is pulse electrochemical etching process of preparing porous luminescent silicon material. The traditional DC current etching process of preparing porous silicon material has some demerits resulting in porous silicon material with imperfect optical characteristics. The pulse electrochemical etching process of the present invention has pulse current introduced, that is, after etching for some period of time the etching current is paused for some time so that the reaction product can diffuse out from the silicon pores formed. The pulse electrochemical etching process can obtain porous silicon material with improved surface interface structure and optical characteristics.
Description
Technical field
The present invention is a kind of novel method that electrochemistry anodic corrosion legal system is equipped with porous silica material.
Background technology
Porous silicon, promptly the porous silicon materials are used as the structure sealing coat in the unicircuit at first, and this is owing to hole in the silicon post in the porous silicon layer exhausts, and the cause of very big resistance is arranged.Porous silicon did not cause people's too many concern at that time.Report for the first time the fifties from twentieth century and to find porous silicon and subsequent nearly 40 years, relevant article only has less than 200 pieces.Nineteen ninety Britain scientist L. T.Canham has found the characteristic of high-level efficiency visible emitting under the porous silicon room temperature, has opened up a new field for total silicon base photoelectricity is integrated, has caused a research boom in scientific circles very soon.People have not only carried out theory and experimental study to the fundamental characteristics of porous silicon, microstructure, formation mechanism, luminous mechanism and carrier transport mechanism etc. as the quantum sponge, and practical devices used carried out attempting widely and exploring, and obtained certain result, as photodiode (LED), silicon based opto-electronics subclass one-tenth, photo-detector, optical waveguides and transmitter etc.
It is galvanic corrosion that the preparation method of porous silicon has a variety of, the most frequently used methods, promptly silicon chip is passed to electric current as anode in the HF acid solution and carries out anodic oxidation.There will be two kinds of situations owing to the alive difference of institute in the HF acid solution for silicon, in current density greater than certain threshold value (with the type of silicon chip, resistivity and corrosive fluid concentration are relevant with factors such as compositions) time, silicon chip will be peeled off by electricity, and when being lower than this threshold value, silicon face will be made of the erratic composition that the silicon post (silicon grain) of countless nanometer scale is formed, and just said " quantum sponge " structure is referred to as porous silicon layer.
The fundamental method of preparation porous silicon is to adopt anode the anodic etching method method.A kind of self-regulating mechanism makes that in the porous silicon forming process, the reaction of corrosive fluid and silicon substrate mainly concentrates on the root in the hole of formation.Though the product that silicon substrate and HF reaction form still has arguement now, produces H in the reaction process
2SiF
6Or the compound of other ionic speciess of some fluosilicics and H
2Obtained certainly.When adopting traditional dc corrosion method corrosion of porous silicon, the fluosilicic compound of generation is deposited on the bottom in hole easily, and H
2Bubble is because surface tension is adsorbed on silicon post surface, and these have all hindered corrosive fluid and have infiltrated through bottom, silicon hole, make chemical reaction become slow and difficult.On the other hand, the reactive deposition thing causes silicon chip resistance to increase, and reaction current density diminishes, and this also is unfavorable for keeping certain reaction speed.These reasons all can cause HF inhomogeneous to the corrosion of silicon, and this comprises two aspects: the silicon pore distribution of porous silicon is inhomogeneous; The interface distributions of porous silicon is inhomogeneous.And then cause the characteristics of luminescence of porous silica material superior inadequately.This just makes us be unfavorable for utilizing the essence of porous silica material---the characteristics of luminescence.
Summary of the invention
The objective of the invention is to make simple, the respond well light-emitting porous silicon preparation methods of a kind of method.
The present invention adopts in the middle of the corrosive process that another preparation method---the method for pulse corrosion prepares porous silicon, i.e. anodic corrosion process is not continuously but carry out the compartment of terrain.Do making reaction product in the intersegmental time of having a rest that does not add corrosion current, can from the silicon hole, diffuse out like this, allow the HF outside the hole also can have one period idle time to be diffused in the hole simultaneously, keep the concentration of corrosive fluid in the hole.Reduced like this since HF at accumulation and the H of the exhausting of hole root, resultant
2Absorption and the obstruction of the antianode oxidation that causes makes next pulse still can concentrate on the hole root to the corrosion of silicon substrate, corrosion position still can the vertical silicon substrate.
Pulse electrochemical anode preparation porous silica material method of the present invention is extremely simple.The cleaning of a slice single-sided polishing is treated that the corrosive silicon chip puts into the etching tank of a tetrafluoroethylene.In etching tank, add the corrosive fluid contain HF,, pulse signal is added in treats to get final product on the corrosive silicon chip for etching tank connects electrode.
Pulse signal of the present invention can be produced by signal generator, its pulsewidth 3.0-100ms, dutycycle 1: (2-10), can adjust in scope according to specific requirement.
The present invention utilizes signal generator and transistor amplifier to produce square-wave signal respectively and then converts current pulse signal to.Transistor amplifier is a prior art circuits.
Pass through transistor amplifier, the square-wave signal that signal generator produces becomes current pulse signal, its intermittent type periodically is added in to be treated on the corrosive silicon sample, cycle is 2-10ms, effectively etching time and intermittent time respectively are half, even the cycle is 5ms, and then effectively etching time and intermittent time are 2.5ms respectively.Corrosion electric current density generally is 1mA/cm
2-90mA/cm
2
During concrete the preparation several pulse square wave signals that need are stored in the different passages of signal generator, on microcomputer, move a cover C++ program then at an easy rate, by choosing predefined passage as GPIB card (National Instrument company model is ASSY182885E-01) control signal producer.Control the time of the passage chosen and the operation of this passage easily by program.The square-wave signal that sends in each passage is added on the silicon chip of etching tank after amplifying through transistor amplifier.Size by the instant observation signal of oscilloscope.Schematic flow sheet is seen Fig. 2.
The present invention has solved the electrochemistry product that can not allow very soon that electrochemical etching method in the past brings to a great extent and has diffused out from porous silicon silicon hole, and even the causing of hole internal corrosion liquid density unevenness obtains the uneven shortcoming of sample surfaces interface structure.Adopt the porous silica material of pulse electrochemical anodic corrosion method preparation to have equally distributed surface arrangement, smooth silicon layer interface the more important thing is that the porous silicon of this method preparation has good optical characteristics.Through a large amount of experiments, the result proves that the pulsed anode etch is a kind of novel method of effective preparation light-emitting porous silicon material.
Description of drawings
Fig. 1 is a pulse corrosion process synoptic diagram of the present invention.
Fig. 2 is an embodiment of the invention synoptic diagram.
Fig. 3 is the surperficial SEM figure that the dc corrosion method obtains sample.
Fig. 4 is the surperficial SEM figure that the pulse corrosion method obtains sample.
1 is computer among the above-mentioned figure, the 2nd, and signal generator has GPIB card, the 3rd, amplifier, the 4th, oscilloscope, the 5th, etching tank, the 6th, adjustable resistance, the 7th, silicon chip between 1,2.
Embodiment
Be size 5V at first, the cycle is 5ms, and dutycycle is 1 passage that 1: 2 square-wave signal is stored to Lecroy 9210 signal generators.Signal generator and computer insert respectively in the slot of microcomputer and signal generator correspondence with a GPIB card connection, the two ends of GPIB card.Write the C++ program then on microcomputer, the port numbers that makes it corresponding control is 1 passage of signal generator, and the time that the setting passage is opened is 3 minutes.This C++ program that brings into operation then, the control signal that program produces make it No. 1 passage and open by GPIB card input signal producer, and signal generator sends the square-wave signal of prior setting.Program begins self-clocking simultaneously.This square-wave signal becomes the big or small 50mA that is by the transistor amplifier change of Fig. 2, and the cycle is 5ms, and dutycycle is that 1: 2 current pulse signal is added on the interior sample of etching tank, and groove internal corrosion liquid is identical with the galvanic current corrosion.Beginning galvanic corrosion sample.Clock time one arrived in 3 minutes, the output of the program automatic shutoff signal in the microcomputer, and 1 pathway closure in the middle of the signal generator is exported square-wave signal no longer outward, and the specimen preparation process is finished.Last needs to take out clean drying up to sample from etching tank and gets final product.
Claims (4)
1, a kind of light-emitting porous silicon preparation methods is characterized in that replacing traditional galvanic current corrosion of porous silicon material with pulsed current.
2, light-emitting porous silicon preparation methods according to claim 1 is characterized in that pulsed current is produced by signal generator, and its pulsewidth is 3.0-100ms, and dutycycle is 1: (2-10).
3, light-emitting porous silicon preparation methods according to claim 1 is characterized in that signal generator and transistor amplifier produce square-wave signal and current pulse signal respectively.
4, light-emitting porous silicon preparation methods according to claim 1 is characterized in that the electric current intermittent type periodically is added on the corrosive silicon sample, and the cycle is 2-10ms, and effectively etching time and intermittent time respectively are half.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115547 CN1436879A (en) | 2003-02-27 | 2003-02-27 | Prepn of porous liminescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115547 CN1436879A (en) | 2003-02-27 | 2003-02-27 | Prepn of porous liminescent material |
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|---|---|
| CN1436879A true CN1436879A (en) | 2003-08-20 |
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ID=27634268
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03115547 Pending CN1436879A (en) | 2003-02-27 | 2003-02-27 | Prepn of porous liminescent material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134737A (en) * | 2011-04-28 | 2011-07-27 | 上海理工大学 | Method for preparing porous silicon |
| CN102623324A (en) * | 2010-12-13 | 2012-08-01 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN104711678A (en) * | 2015-02-04 | 2015-06-17 | 杭州电子科技大学 | Method for preparing silicon nanostructure material under alternative electric fields |
| CN106517080A (en) * | 2016-10-12 | 2017-03-22 | 湖南文理学院 | Novel method for enhancing stability of physical microstructure and optical properties of nano-porous silicon |
| CN106653593A (en) * | 2016-10-26 | 2017-05-10 | 湖南文理学院 | Method for improving uniformity of longitudinal physical structure and stability of optical properties of porous silicon |
| CN108368636A (en) * | 2015-12-11 | 2018-08-03 | 奈克斯沃夫有限公司 | Device and method for unilateral etching semiconductor substrate |
-
2003
- 2003-02-27 CN CN 03115547 patent/CN1436879A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623324A (en) * | 2010-12-13 | 2012-08-01 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN102623324B (en) * | 2010-12-13 | 2014-12-10 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN102134737A (en) * | 2011-04-28 | 2011-07-27 | 上海理工大学 | Method for preparing porous silicon |
| CN104711678A (en) * | 2015-02-04 | 2015-06-17 | 杭州电子科技大学 | Method for preparing silicon nanostructure material under alternative electric fields |
| CN104711678B (en) * | 2015-02-04 | 2017-07-04 | 杭州电子科技大学 | A kind of method that silicon nanostructure material is prepared under alternating electric field |
| CN108368636A (en) * | 2015-12-11 | 2018-08-03 | 奈克斯沃夫有限公司 | Device and method for unilateral etching semiconductor substrate |
| CN108368636B (en) * | 2015-12-11 | 2021-09-24 | 奈克斯沃夫有限公司 | Apparatus and method for single-sided etching of semiconductor substrates |
| CN106517080A (en) * | 2016-10-12 | 2017-03-22 | 湖南文理学院 | Novel method for enhancing stability of physical microstructure and optical properties of nano-porous silicon |
| CN106517080B (en) * | 2016-10-12 | 2018-07-10 | 湖南文理学院 | Improve the new method of nano-structure porous silicon physics micro-structure and optical characteristics stability |
| CN106653593A (en) * | 2016-10-26 | 2017-05-10 | 湖南文理学院 | Method for improving uniformity of longitudinal physical structure and stability of optical properties of porous silicon |
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