CN1824833A - Porous indium phosphide barrier layer, corrosion liquid of porous indium phosphide and use method - Google Patents
Porous indium phosphide barrier layer, corrosion liquid of porous indium phosphide and use method Download PDFInfo
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- CN1824833A CN1824833A CN 200510011351 CN200510011351A CN1824833A CN 1824833 A CN1824833 A CN 1824833A CN 200510011351 CN200510011351 CN 200510011351 CN 200510011351 A CN200510011351 A CN 200510011351A CN 1824833 A CN1824833 A CN 1824833A
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Abstract
This invention relate to a multi-hole indium phosphide barrier layer and its corrosive liquor and its using method. It includes the mixed liquor of hydrobromic acid, nitric acid and water. The weight amount is that hydrobromic acid: 1-2, water 10-20. the procedures are that 1: a multi-hole indium phosphide material is selected, 2: the multi-hole indium phosphide material is soaked into the mixed liquor said in claim of right 1, 3: the barrier layer of the indium phosphide surface and part of the multi-hole indium phosphide layer is eroded, so the material is thinned.
Description
Technical field
The present invention is a technical field of semiconductors, particularly about the removal method on the surperficial blocking layer that generates of porous indium phosphide and the thining method of porous indium phosphide, specifically, be about removing porous indium phosphide surface barrier and the corrosive fluid of attenuate porous indium phosphide and the using method of this corrosive fluid.
Background technology
Discovery by strong visible light on the porous silicon of electrochemical etching method preparation has caused the very big interest of people to porous semi-conductor material.People are to porous SiC in recent years, SiGe, and GaP, GaAs, GaN, porous semiconductor compounds such as InP have carried out many researchs.Wherein, relatively be typically with Al
2O
3Film is done the large-scale self-organizing growth that mask prepares, the nano material array of queueing discipline, as carbon nano pipe array; Si, the GaAs, the GaN nanohole array that adopt reactive ion etching to get are by metal and the semi-conductive quantum dot array that evaporation and etching form, two-dimensional transversal superstructure etc.
For Si and III-V compound semiconductor materials, the vesicular structure that adopts electrochemical etching method to obtain distributes at random poor controllability, the out-of-shape in hole.And can obtain regular distribution, arranged vertical by galvanic corrosion InP, the aperture is about the hole of 100nm.
Therefore galvanic corrosion is used in indium phosphide and relevant porous material preparation because damage is low.Recent years, the research of a lot of porous indium phosphide structures that the galvanic corrosion indium phosphide obtains in electrolysis of hydrochloric acid liquid has been arranged.At Jpn.J.Appl.Phys.Vol 41 (2002), pages 977-981, February 2002, make the mask molecular beam epitaxial growth with the nanoporous indium phosphide among the Tesuro HIRANO et al. and obtained InP base InGaAs quantum well and quantum dot array.
Yet, although the various countries scholar has launched a series of researchs to porous indium phosphide, and obtained some preliminary achievements, the blocking layer that forms for the surface of porous indium phosphide in the initial stage of galvanic corrosion process does not still have good method to remove at present.This barrier layer surface pattern is intricate, the character extreme difference, and for do template growth quantum dot, line with porous indium phosphide, the further research and the application of well structure and photonic crystal etc. have caused obstacle.Bibliographical information H is arranged
2SO
4: H
2O: H
2O
2=3: 1: 1, etching time removed this irregular blocking layer (Physica E Vol 9 (2001), pages 723-727, Aimin Liu et al.) in 30 seconds, but the porous indium phosphide surface of adopting this method to obtain is inhomogeneous, and makes easily that porous layer is whole to come off.This patent has solved this problem, can remove the blocking layer on porous indium phosphide surface and the thickness of attenuate porous indium phosphide efficiently, equably by no electrolysis wet etching.
Summary of the invention
One object of the present invention is, the corrosive fluid of a kind of porous indium phosphide barrier layer and porous indium phosphide is provided, and this corrosive fluid does not bring detrimentally affect to semiconductor technology, and can be efficiently, equably the blocking layer on porous indium phosphide surface is corroded.
Another object of the present invention is, the using method of a kind of porous indium phosphide barrier layer and porous indium phosphide corrosive fluid is provided, and this method is not brought detrimentally affect to semiconductor technology, and can be efficiently, equably porous indium phosphide is carried out attenuate.
According to purpose of the present invention, the invention provides the corrosive fluid of a kind of porous indium phosphide barrier layer and porous indium phosphide, it is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20.
The preparation method of the corrosive fluid of a kind of porous indium phosphide barrier layer of the present invention and porous indium phosphide is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20;
Hydrogen bromide, nitric acid, water are mixed stirring.
Wherein this mixing solutions time of depositing more than one month can use, to guarantee the homogeneity of mixing solutions.
Wherein the corrosive nature of this mixing solutions is relevant with the shelf-time and the temperature of this mixing solutions, and the corrosive nature of mixing solutions was directly proportional with the shelf-time, and the temperature condition of corrosive fluid is set in the scope of normal temperature.
According to another object of the present invention, the using method of a kind of porous indium phosphide barrier layer of the present invention and porous indium phosphide corrosive fluid is characterized in that, comprises the steps:
Step 1: get a porous indium phosphide material;
Step 2: the porous indium phosphide material is immersed in described this mixing solutions of claim 1;
Step 3: erode the blocking layer and the partially porous phosphorization phosphide indium layer on porous indium phosphide surface, with porous indium phosphide material attenuate.
The time that wherein the porous indium phosphide material is immersed in the mixing solutions is 30 seconds to 600 seconds, to erode corresponding thickness.
Description of drawings
For further specifying technology contents of the present invention, below in conjunction with example and accompanying drawing describes in detail as after, wherein:
When Fig. 1 corrodes porous indium phosphide surface barrier and porous indium phosphide for using corrosive fluid of the present invention, the mutual relationship figure of its depth of corrosion and etching time;
Fig. 2 is the cross section shape appearance figure of the porous indium phosphide of employing electrochemical etching method acquisition;
Fig. 3 A-3B is for using corrosive fluid the wet method of the present invention manually cross section and the surface topography map of 60 seconds porous indium phosphide of corrosion;
Fig. 4 A-4B is for using corrosive fluid the wet method of the present invention manually cross section and the surface topography map of 150 seconds porous indium phosphide of corrosion;
Fig. 5 A-5B is for using the cross section and the surface topography map of 180 seconds porous indium phosphide of the static corrosion of corrosive fluid wet method of the present invention;
Fig. 6 is the surface topography map of the porous indium phosphide of the static corrosion of sulfuric acid corrosion liquid wet method after 120 seconds.
Embodiment
The corrosive fluid of a kind of porous indium phosphide barrier layer of the present invention and porous indium phosphide is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20.
The preparation method of the corrosive fluid of a kind of porous indium phosphide barrier layer of the present invention and porous indium phosphide is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20;
Hydrogen bromide, nitric acid, water are mixed stirring.
Wherein this mixing solutions time of depositing more than one month can use, to guarantee the homogeneity of mixing solutions.
Wherein the corrosive nature of this mixing solutions is relevant with the shelf-time and the temperature of this mixing solutions, and the corrosive nature of mixing solutions was directly proportional with the shelf-time, and the temperature condition of corrosive fluid is set in the scope of normal temperature.
The using method of a kind of porous indium phosphide barrier layer of the present invention and porous indium phosphide corrosive fluid is characterized in that, comprises the steps:
Step 1: get a porous indium phosphide material;
Step 2: the porous indium phosphide material is immersed in described this mixing solutions of claim 1;
Step 3: erode the blocking layer and the partially porous phosphorization phosphide indium layer on porous indium phosphide surface, with porous indium phosphide material attenuate.
The time that wherein the porous indium phosphide material is immersed in the mixing solutions is 30 seconds to 600 seconds, to erode corresponding thickness.
Below corrosive fluid of the present invention and caustic solution are elaborated, Fig. 1 has provided the mixing solutions Hydrogen bromide with Hydrogen bromide and nitric acid: 1, nitric acid: 1, water: when 10 corrosion porous indium phosphide surface barriers and porous indium phosphide, the mutual relationship of its depth of corrosion and etching time; As can see from Figure 1, though corrosion speed is slower in the blocking layer stage, whole process corrosion speed basically identical.In addition, depth of corrosion is along with the prolongation of etching time is linear increase.
Wherein, this porous indium phosphide is by being 1 * 10 to doping content
18Cm
3, thickness is that S-dopped InP (100) wafer of 500 μ m carries out galvanic corrosion and obtains, its aperture is about 200nm, hole depth is about 4.66 μ m, pattern is (the non-straight hole of wherein going up face thickness 0.95 μ m partly is the blocking layer) as shown in Figure 2;
Wherein, the condition for preparing this porous indium phosphide is:
Polarizing voltage: 9.0V;
Etching time: 11s;
Corrosive fluid: 1M HCl (200ml)+3mlHNO
3
The condition of above-mentioned preparation porous indium phosphide is not unique, can do suitable change to each parameter according to actual needs.
It is Hydrogen bromide that the porous indium phosphide that makes under the above-mentioned galvanic corrosion condition is immersed weight part: 1, nitric acid: 1, water: in 10 the corrosive fluid,, then the degree of porous indium phosphide surface barrier removal or the thickness of porous indium phosphide attenuate are measured with hand wobble or static corrosion.
3A-3B in conjunction with the accompanying drawings at first, provides Hydrogen bromide: 1, and nitric acid: 1, water a: example of 10 corrosive fluid corrosion porous indium phosphide surface barrier.
The porous indium phosphide that obtains is under these conditions immersed Hydrogen bromide: 1, nitric acid: 1, water: in 10 the corrosive fluid, and use hand wobble, then measure the thickness of porous indium phosphide attenuate.Porous indium phosphide is at Hydrogen bromide: 1, nitric acid: 1, water: in 10 the corrosive fluid, temperature is 12 ℃, and use hand wobble, just eroded the surface barrier that thickness is 0.96 μ m in 60 seconds fast, Fig. 3 A-3B has provided porous indium phosphide cross section and the surface topography behind the blocking layer of removing that obtains under this no electrolysis wet etching condition, can see that it has an even surface, corrodes evenly.
As an example, above-described is that shelf-time with corrosive fluid is 5 months, and temperature adopts 12 ℃ situation, might not be limited to condition given among the present invention in the actually operating.Comparatively ideal is Hydrogen bromide: 1, and nitric acid: 1, water: the shelf-time of 10 corrosive fluid was greater than one month, because if the shelf-time is too short, corrosion speed is then unstable; Temperature generally adopts room temperature to get final product.
Porous indium phosphide after the corrosion washes repeatedly with deionized water, and dries up with nitrogen.
Provide Hydrogen bromide again below in conjunction with Fig. 4 A-4B: 1, nitric acid: 1, water: 10 corrosive fluid corrosion porous indium phosphide surface barrier and another example of porous indium phosphide.
Equally the resulting porous indium phosphide wafer of above-mentioned condition is immersed Hydrogen bromide: 1, nitric acid: 1, water: in 10 the corrosive fluid, and be 8 words hand wobble corrosive fluid, then measure the thickness of porous indium phosphide attenuate.Porous indium phosphide is at Hydrogen bromide: 1, and nitric acid: 1, water: in 10 the corrosive fluid, temperature is 12 ℃, manually under the corrosive condition, is just eroded its surperficial blocking layer 2.01 μ m fast in 150 seconds, it has an even surface, corrodes evenly.This example erodes the blocking layer on porous indium phosphide surface earlier, corrodes the porous indium phosphide layer afterwards again, and the blocking layer that not only can remove the porous indium phosphide surface can be controlled the thickness of porous indium phosphide relatively.
Porous indium phosphide after the corrosion washes repeatedly with deionized water, and dries up with nitrogen.
Below again in conjunction with Fig. 5 A-5B explanation Hydrogen bromide: 1.9, nitric acid: 1.9, water: 20 corrosive fluid corrodes the example of porous indium phosphide surface passivation layer and porous indium phosphide under static corrosive condition.
Equally the resulting porous indium phosphide wafer of aforementioned electric chemical corrosion condition is immersed Hydrogen bromide: 1, nitric acid: 1, water: in 10 the corrosive fluid, and static corrosion, then measure the thickness of porous indium phosphide attenuate.Porous indium phosphide is at Hydrogen bromide: 1.9, and nitric acid: 1.9, water: in 20 the corrosive fluid, temperature is 16 ℃, under the static corrosive condition, is just eroded its surperficial passivation layer 2.01 μ m fast in 180 seconds, it has an even surface, corrodes evenly, shown in Fig. 5 A-5B.
Porous indium phosphide after the corrosion washes repeatedly with deionized water, and dries up with nitrogen.
Except top three examples, for ease of comparing, Fig. 6 gives the surface topography that adopts sulphuric acid soln corrosion porous indium phosphide barrier layer to obtain.The volume ratio sulfuric acid of sulphuric acid soln wherein: 1, hydrogen peroxide: 1, water: 4, the time of no electrolysis wet etching is 120 seconds, room temperature, static corrosion.Can observe from Fig. 6, sulfuric acid corrosion liquid is very slow to the corrosion speed of porous indium phosphide, and effect is relatively poor.And find in the experiment that sulfuric acid corrosion liquid is difficult to remove the blocking layer of porous indium phosphide.
Claims (6)
1, the corrosive fluid of a kind of porous indium phosphide barrier layer and porous indium phosphide is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20.
2, the preparation method of the corrosive fluid of a kind of porous indium phosphide barrier layer and porous indium phosphide is characterized in that, comprising:
The mixing solutions of Hydrogen bromide and nitric acid and water, the weight part of this mixing solutions is:
Hydrogen bromide: 1-2;
Nitric acid: 1-2;
Water: 10-20;
Hydrogen bromide, nitric acid, water are mixed stirring.
3, the preparation method of the corrosive fluid of porous indium phosphide barrier layer according to claim 2 and porous indium phosphide is characterized in that, wherein this mixing solutions time of depositing more than one month can use, to guarantee the homogeneity of mixing solutions.
4, the preparation method of the corrosive fluid of corrosion porous indium phosphide surface barrier according to claim 2 and porous indium phosphide, it is characterized in that, wherein the corrosive nature of this mixing solutions is relevant with the shelf-time and the temperature of this mixing solutions, the corrosive nature of mixing solutions was directly proportional with the shelf-time, and the temperature condition of corrosive fluid is set in the scope of normal temperature.
5, the using method of a kind of porous indium phosphide barrier layer and porous indium phosphide corrosive fluid is characterized in that, comprises the steps:
Step 1: get a porous indium phosphide material;
Step 2: the porous indium phosphide material is immersed in described this mixing solutions of claim 1;
Step 3: erode the blocking layer and the partially porous phosphorization phosphide indium layer on porous indium phosphide surface, with porous indium phosphide material attenuate.
6, the using method of corrosion porous indium phosphide surface barrier according to claim 5 and porous indium phosphide corrosive fluid, it is characterized in that, the time that wherein the porous indium phosphide material is immersed in the mixing solutions is 30 seconds to 600 seconds, to erode corresponding thickness.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111300260A (en) * | 2020-02-19 | 2020-06-19 | 中国科学院微电子研究所 | Polishing and thinning device and polishing and thinning method |
| CN114540033A (en) * | 2022-01-13 | 2022-05-27 | 北京通美晶体技术股份有限公司 | Indium phosphide thinning corrosion solution and application thereof |
-
2005
- 2005-02-25 CN CN 200510011351 patent/CN1824833A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111300260A (en) * | 2020-02-19 | 2020-06-19 | 中国科学院微电子研究所 | Polishing and thinning device and polishing and thinning method |
| CN114540033A (en) * | 2022-01-13 | 2022-05-27 | 北京通美晶体技术股份有限公司 | Indium phosphide thinning corrosion solution and application thereof |
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