CN103762274B - A kind of indium surface-treated method - Google Patents
A kind of indium surface-treated method Download PDFInfo
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- CN103762274B CN103762274B CN201410021010.3A CN201410021010A CN103762274B CN 103762274 B CN103762274 B CN 103762274B CN 201410021010 A CN201410021010 A CN 201410021010A CN 103762274 B CN103762274 B CN 103762274B
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- indium
- plasma
- post
- oxide layer
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 53
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 abstract description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000003705 background correction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Plasma Technology (AREA)
- Drying Of Semiconductors (AREA)
Abstract
The present invention discloses a kind of method removing indium surface oxide layer.This technical scheme specifically comprises: cleaning plasma chamber and plasma treatment two step.The advantage of the method is can not only remove surface oxide layer and can effectively prevent the unsalted surface of indium to again be oxidized.
Description
Technical field
The present invention relates to metal surface treatment technology in microelectronic technique field, be specifically related to a kind of indium surface-treated process.
Background technology
Infrared focal plane array is the core component of modern imaging system, and it is consisted of interconnection detector and reading circuit, and schematic diagram as shown in Figure 1.Therefore, interconnection process is directly connected to performance and the rate of finished products of focal plane device.To the technical requirement that interconnection material is selected be: first need to all detection unit and reading circuit input provide machinery to be completely connected with electricity; Next needs the thermal expansion mismatch cushioning detector and reading circuit under low temperature.The melting temperature of indium metal is 156 DEG C, boiling temperature 2080 DEG C, and when vapour pressure is 1.33Pa, its evaporating temperature is 952 DEG C, and the indium layer thermal stress that vacuum evaporation produces is less.Indium is a kind of low-melting-point soft metal, and at room temperature intrinsic stress can disappear very soon, is less than 5 × 10
2n/cm
2 [1].Therefore, indium becomes desirable interconnection material.
Infrared focal plane array is generally interconnected by indium post, requires: 1) indium post height is greater than 5 μm; 2) diameter is little as far as possible; 3) evenness is high; 4) smooth surface, not oxidized [2].But indium is as so-called " valve metal ", in wet environment, naturally generate oxide layer [3].And from room temperature 25 DEG C to boiling point 1807 DEG C, thermodynamically indium oxide is all than indium metal more stable [4].In order to remove the oxide layer on indium post surface, the method that first researcher adopts is hydrochloric acid solution [5].By reaction
In
2O
3(s)+6H
+(aq)+6e
-→2In(m)+3H
2O(aq)
Hydrochloric acid, while removal surface oxide layer, also reacts with lower floor's indium
2In+6HCl→2InCl
3+3H
2
While the anisotropic of wet etching causes indium post itself to be cut down, appearance becomes and is uneven, and reduces the mechanical strength of interconnection.
By calculating the gibbs free energy change that reductive hydrogen and indium react, discovery, when humidity and hydrogen ratio are in a certain value determined value, can thermodynamically reach indium oxide and indium balances.The redox curve of what accompanying drawing 2 provided is indium and indium oxide systems thermodynamics, wherein, reduced zone drifts about along with the increase of humidity.Interval corresponding to the humidity left side represents between thermodynamics zoneofoxidation, and the right represents between reducing zone; Curve then represents the equilibrium state of indium and indium oxide.
But the technological requirement temperature removing indium oxide with molecular hydrogen at least just can have significant reaction rate more than 380 DEG C.IRFPAs can not bear this temperature.Although adopt hydrogen atom greatly can reduce reaction temperature [5], also there is again oxidized problem [6].Researchers have been inspired to select the exploration [7,8] of CH4/H2 plasma etching to the research of ITO selective etch.Wherein with the result of study of F.Greer significantly [9].They adopt the method for two steps etchings, reduce etching to indium post itself successfully removing indium oxide simultaneously.But the method also fails to prevent clean indium again oxidized.
List of references involved in literary composition is as follows:
[1] Huang Jiangping, Yang Chunli, Li Li, Yang Dengquan, Zhang Lihua, Li Yuying, infrared technique, 25(6), 2003, p54.
[2] Yang Chunli, Huang Jiangping, Li Li, Yang Dengquan, Zhang Lihua, Li Yuying, infrared technique, 26(1), 2004, p67.
[3]S.Omanovic,M.Methikos-Hukovic,ThinSolidFilms,266,1995,p31.
[4]J.Kim,H.Schoeller,J.Cho,andS.Park,JournalofElectronicMaterials,37(4),2008,p483.
[5]Y.Kim,J.Choi,K.Choi,H.LeeandC.Kim,Proc.SPIE,3061,1997,p60.
[6]GilesHumpstonandDvidM.Jacobson,Principlesofsoldering,ThematerialsInformationSociety,MatertialsPark,OH,2004.
[7]I.Adesida,D.G.Ballegeer,J.W.Seo,A.Ketterson,H.Chang,andT.Gessert,J.Vac.Sci.Technol.B9.3551(1991)
[8]R.J.Saia,R.F.Kwasnick,andC.Y.Wei,J.Electrochem.Soc.,138,493(1991).
[9]F.Greer,M.Dickie,R.P.Vasquez,T.J.Jones,M.E.HoenkandS.Nikzad,J.Vac.Sci.Technol.B,27,2009,2132.
Summary of the invention
The object of this invention is to provide a kind of method of modifying indium post and indium pellet surface, solve the problem of interconnection indium post, indium pellet oxidized and secondary oxidation in atmosphere.
The processing step of the inventive method is as follows:
1). the reaction cavity of plasma equipment carries out O
2, O
2and SF
6two steps cleaning;
2). the pending sample containing indium post or indium pellet is put in plasma apparatus, after equipment vacuum is qualified, carries out biography sheet; With the CH that flow-rate ratio is 0.5 ~ 1:0.5 ~ 1:0.5 ~ 1:1 ~ 1.6
4, H
2, Ar and SF
6mixed gas plasma carries out sample, and process processing power is less than 75W.
Wherein: the Ar in mist can use N
2replace, SF
6cF can be used
4substitute.
The invention has the advantages that method is simple, and do not affect indium post/spherical looks and performance, with existing microelectronic technique line, there is good compatibility, the following process of indium post/ball sample is not had an impact.Effectively can remove the oxide layer on indium post/ball surface and prevent it again oxidized.
Accompanying drawing explanation
Fig. 1 is infrared focal plane array schematic diagram.
Fig. 2 is the curve that indium and indium oxide system change with humidity.
Scheming (1) in Fig. 3 is indium post surface Scanning Electron microscope shape appearance figure before treatment, and figure (2) is the indium post surface Scanning Electron microscope shape appearance figure after process.
Fig. 4 is the full spectrum of the x-ray photoelectron spectroscopy on indium post surface before and after process.
Fig. 5 (a) is the x-ray photoelectron spectroscopy of indium post surface high-resolution O1s before process, and (b) is the x-ray photoelectron spectroscopy of indium post surface high-resolution O1s after process.
Embodiment
Case study on implementation 1
The present invention adopts induced-coupled plasma ICP system to complete, and processing step is as follows:
(1) O is carried out to the reaction cavity of equipment
2, O
2and SF
6two step plasma clean;
(2) the indium post sample prepared is put in equipment, waits for that vacuum carries out biography sheet after qualified; With the CH of 0.5:0.5:0.5:1
4/ H
2/ Ar/SF
6plasma processes sample, and processing power and body flow thereof all need to ensure that indium cylindricality looks are unaffected;
Case study on implementation 2
The present invention adopts induced-coupled plasma ICP system to complete, and processing step is as follows:
(1) O is carried out to the reaction cavity of equipment
2, O
2and SF
6two step plasma clean;
(2) the indium post sample prepared is put in equipment, waits for that vacuum carries out biography sheet after qualified; With the CH of 0.8:0.8:0.8:1
4/ H
2/ Ar/SF
6plasma processes sample, and processing power and body flow thereof all need to ensure that indium cylindricality looks are unaffected;
Case study on implementation 3
The present invention adopts induced-coupled plasma ICP system to complete, and processing step is as follows:
(1) O is carried out to the reaction cavity of equipment
2, O
2and SF
6two step plasma clean;
(2) the indium post sample prepared is put in equipment, waits for that vacuum carries out biography sheet after qualified; With the CH of 1:1:1:1.6
4/ H
2/ Ar/SF
6plasma processes sample, and processing power and body flow thereof all need to ensure that indium cylindricality looks are unaffected;
By scanning electron microscopy, morphology characterization is carried out to the indium post sample before and after process, as shown in Figure 3.As can be seen from the figure plasma treatment does not produce obviously impact to indium cylindricality looks.Accompanying drawing 4 is that the x-ray photoelectron spectroscopy of indium post sample before and after process is composed entirely, has obvious S1s, S2p and F1s peak, successfully modified indium post surface after plasma treatment is described in the spectral line after process.
Fig. 5 (a) is the x-ray photoelectron spectroscopy collection of illustrative plates of indium post sample high-resolution O1s before process, and (b) is the x-ray photoelectron spectroscopy of indium post surface high-resolution O1s after process.By background correction Voigt peak-fit processing, can with two of being positioned at 531.7eV and 530.5eV unimodal come the O peak of matching two samples.These two unimodal in the corresponding hydrogen-oxygen thing of adsorption in high-octane peak, be expose inevitable in atmosphere, low-energy peak position has been then corresponding surface oxidation indium.After plasma treatment, low-yield peak position percentage is down to 10.8% from before treatment 42.2% rapidly, represents effective removal of oxide on surface, and eliminates the interference reoxidized.
Claims (2)
1. remove a method for indium surface oxide layer, it is characterized in that comprising the following steps:
1). the reaction cavity of plasma equipment carries out O
2, O
2and SF
6two steps cleaning;
2). the pending sample containing indium post or indium pellet is put in plasma apparatus, after equipment vacuum is qualified, carries out biography sheet; Be (0.5 ~ 1) by flow-rate ratio: (0.5 ~ 1): (0.5 ~ 1): the CH of (1 ~ 1.6)
4, H
2, Ar and SF
6mixed gas plasma processes sample, and processing power is less than 75W.
2. a kind of method removing indium surface oxide layer according to claim 1, is characterized in that: step 2) described in mist in Ar N
2replace, SF
6use CF
4substitute.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410021010.3A CN103762274B (en) | 2014-01-17 | 2014-01-17 | A kind of indium surface-treated method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410021010.3A CN103762274B (en) | 2014-01-17 | 2014-01-17 | A kind of indium surface-treated method |
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| Publication Number | Publication Date |
|---|---|
| CN103762274A CN103762274A (en) | 2014-04-30 |
| CN103762274B true CN103762274B (en) | 2015-11-25 |
Family
ID=50529481
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| Country | Link |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561593A (en) * | 1994-01-27 | 1996-10-01 | Vicon Enterprises, Inc. | Z-interface-board |
| CN1587958A (en) * | 2004-07-27 | 2005-03-02 | 中国科学院上海技术物理研究所 | Indium pole pelletizing method of infrared focal plane detector |
| CN1949508A (en) * | 2006-11-08 | 2007-04-18 | 中国科学院上海技术物理研究所 | Infrared focal plane detector with antireflective convergence microlens and microlens preparing method |
| CN102881607A (en) * | 2012-09-27 | 2013-01-16 | 中国科学院长春光学精密机械与物理研究所 | Novel focal plane array electrical interconnection process |
-
2014
- 2014-01-17 CN CN201410021010.3A patent/CN103762274B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561593A (en) * | 1994-01-27 | 1996-10-01 | Vicon Enterprises, Inc. | Z-interface-board |
| CN1587958A (en) * | 2004-07-27 | 2005-03-02 | 中国科学院上海技术物理研究所 | Indium pole pelletizing method of infrared focal plane detector |
| CN1949508A (en) * | 2006-11-08 | 2007-04-18 | 中国科学院上海技术物理研究所 | Infrared focal plane detector with antireflective convergence microlens and microlens preparing method |
| CN102881607A (en) * | 2012-09-27 | 2013-01-16 | 中国科学院长春光学精密机械与物理研究所 | Novel focal plane array electrical interconnection process |
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| Publication number | Publication date |
|---|---|
| CN103762274A (en) | 2014-04-30 |
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