CN87107819A - The yttrium oxide constituent that evaporation is used and the manufacture method of antireflection film - Google Patents
The yttrium oxide constituent that evaporation is used and the manufacture method of antireflection film Download PDFInfo
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- CN87107819A CN87107819A CN87107819.8A CN87107819A CN87107819A CN 87107819 A CN87107819 A CN 87107819A CN 87107819 A CN87107819 A CN 87107819A CN 87107819 A CN87107819 A CN 87107819A
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- evaporation
- yttrium oxide
- antireflection film
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- 238000001704 evaporation Methods 0.000 title claims abstract description 24
- 230000008020 evaporation Effects 0.000 title claims abstract description 23
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000470 constituent Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 8
- 238000002310 reflectometry Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012887 quadratic function Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- H01L31/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The present invention relates to a kind of yttrium oxide constituent that titanium oxide and zirconic evaporation are used that contains, and manufacturing is used for the antireflection film that the III-V compound semiconductor as silicon or GaAs is used as deposition material with this constituent, and this antireflection film can make by the surface albedo on the evaporation thing almost nil.And because the timeliness variation is little, can prolong opening time.
Description
The present invention relates to the yttrium oxide constituent that evaporation uses and the manufacture method of antireflection film.
As Appl.Phys.Lett Vo L.47, NO.5, the 450th page and Applied Optics, Vol.23, NO.1, the 161st page go up explanation like that, people use ZrO usually
2Or Si
3N
4As deposition material the element of being made by Si or Ga As is carried out forming of antireflection film.This is because the specific refractory power of these elements is 3.5, requires the refractive index value of antireflection film to be in theory
＝1.87。The deposition material of the big activation of specific refractory power satisfied 1.87 is ZrO
2And Si
3N
4The blocky specific refractory power of these materials respectively is 2.05 and 1.98, yet under situation about using as film, by adjusting the evaporation condition, can reach refractive index n=1.87.Be presented at T.L.Paoli about this fact, Appl.Phys.Lett.47(5), 450(1985), the 450th page and G.Eisens-tein, Appl.Optics, 23(1), and 161(1984), on the 162nd page.Using ZrO in the past
2Or Si
3N
4When such evaporation constituent generates the antireflection film that is used for Si or Ga As, promptly enable reflectivity and reach zero, but, may not just can be satisfied with owing to the secular variation characteristic of reflectivity concerns.Therefore, although its initial stage characteristic can meet the demands, there is timeliness variation shortcoming greatly in constituent always.
Yttrium oxide constituent of the present invention for addressing the above problem, as to provide a kind of evaporation to use.In addition, another purpose provides method and material stabile on a kind of manufacturing chemistry, good endurance, that reflection prevents the vapor-deposited film of excellent property.
Relating to evaporation of the present invention is a kind of titanium oxide and zirconic constituent of containing with the yttrium oxide constituent.In addition, the manufacture method that relates to the antireflection film of another invention has been to use and has contained titanium oxide and the zirconic evaporation method with yttrium oxide.
With evaporation of the present invention yttrium oxide constituent, can obtain the film that specific refractory power can approach theoretic required value 1.87, and the timeliness variation has diminished also.
Embodiment
When research is used for the necessary deposition material of antireflection film of GaAs or Si for generation, understood fully as timeliness to change little material, Y
2O
3It is a kind of excellent material.Yet, because its specific refractory power is slightly a little bit smaller, not only, therefore to avoid using separately Y
2O
3
Therefore, Y
2O
3Get up with the combinations of substances that specific refractory power is big, to obtain desirable material.When wanting to obtain hybrid films, wish that various materials vapour pressure separately is approaching.That is because the component of deposition material can change in evaporation.Because in 2300 ℃～2600 ℃ temperature range, Y
2O
3And ZrO
2Vapour pressure almost equate, so with Y
2O
3And ZrO
2As main compounding substances, for the purpose of the revisal specific refractory power, add some TiO again
2Can alleviate ZrO
2The ununiformity of peculiar component at film thickness direction.
When making surface albedo R be zero, surface albedo R is with the variation minimum of the refractive index n f change of film.That is to say that making surface albedo is zero to be to obtain the prerequisite that timeliness changes little antireflection film.
As the formula (1), surface albedo R is the quadratic function of the refractive index n f of film:
R＝（ (no·ns-nf
2)/(no·ns+nf
2) )
2……（1）
In the formula, n
oBe the specific refractory power of incident medium, when incident medium is air, n
o=1.00.n
sBe the specific refractory power of substrate, when substrate is Ga As, n
s=3.5.
The simplification of (1) formula has just been become (2) formula:
R∝（nf-1.87）
2……（2）
The variation that surface albedo R causes with the variation of the refractive index n f of film can be regarded as nf as the formula (3) more near 1.88, and velocity of variation is more little.
(dR)/(dnf) ∝2（nf-1.87） ……（3）
Use Y separately
2O
3Resulting surface albedo R(%) as shown in table 1 as can be seen from Figure 1.
Table 1
As design a kind of hybrid films, and the specific refractory power of gained can be met the following conditions, promptly surface albedo R is below 0.25%, then according to Fig. 1, formula (4) can be set up.
1.732＜nf＜2.048 ……（4）
Again, can satisfy surface albedo and be the nf below 0.05%, formula (5) can be set up as can be seen from Figure 2:
1.775＜nf＜1.992 ……（5）
According to Fig. 3, can satisfy the TiO of (4) formula or (5) formula
2And ZrO
2Blend level as shown in table 2.
Table 2
Embodiment 1
Make it thorough mixing after in yttrium oxide, adding weight ratio and be 10% zirconium white, 1% titanium oxide, with 500kg/cm
2The pressure impact briquetting after, thereby under about 1300 ℃, carry out the tablet ( Block レ Star ト) that about 3 hours sintering obtains evaporation test usefulness.Then this reagent is inserted in the electron beam gun that is configured in the evaporation coating device.Be vented to vacuum tightness and reach 5 * 10
-5Behind the Torr, also note the top of glass substrate and the on-chip situation of Ga As, the output rating of electron beam gun is strengthened on the limit, and the temperature that improves tablet makes its fusing, carries out evaporation again under 300 ℃ of substrate temperatures and reaches nd=120nm until blooming.By the vapor-deposited film of evaporation this reagent on glass substrate, its refractive index n=1.84, there is not absorption yet, clinging power to Ga As substrate is big, and chemically stable, good endurance, be almost 0% at the on-chip surface albedo of Ga As, and prevent to have obtained extremely satisfied film with material as the reflection that can keep its initial stage characteristic in long-time.
After adding weight ratio and be 20% zirconium white and 1.5% titanium oxide in yttrium oxide, the method same with the foregoing description obtains tablet.With the method same with the foregoing description, under 120 ℃ of substrate temperatures, carry out the result of evaporation on the end face of the laser diode of Ga As-Ga Al As system, the reflectivity of laser emitting surface almost becomes zero, begins to demonstrate the SLD(superluminescent diode) characteristic.
The sustainable long period of this characteristic.
Comparative example
In yttrium oxide, add weight ratio and be 20% zirconium white and 8% titanium oxide, obtain tablet with the foregoing description 1 same method.Getting substrate temperature is 120 ℃, and other condition is carried out evaporation with method similarly to Example 2 on the end face of the laser diode of Ga As-Ga Al As system.Its result is, it is about 1.2% that surface albedo shows, fails to obtain the characteristic as the SLD element.
From the result of last note as seen, evaporation is 0～90% weight with the zirconic amount that is contained in the yttrium oxide constituent, and 0～80% weight is for well; The amount of the titanium oxide that contains is 0～7.3% weight, and 0.5～4.8% weight is for well.
As by another suitable example of evaporation thing, can on the photodiode of making by the Si semi-conductor, photorectifier etc., be used as antireflection film.
In the above-described embodiments, be that the method with regard to electron beam gun heating describes, but the method that is used as the target of sputter also can be expected same effect.
As mentioned above, because the semi-conductive specific refractory power that the present invention is made by Si or Ga As generates antireflection film and the mixed component of being made up of yttrium oxide, zirconium white, titanium oxide is made deposition material, so can make by the surface albedo on the evaporation thing almost nil.In addition, because the timeliness variation is little, can prolong opening time.
Be simple declaration below to accompanying drawing.
Fig. 1 and Fig. 2 are the synoptic diagram of the relation of the specific refractory power of film and surface albedo, and Fig. 3 is TiO
2Combined amount and the synoptic diagram of the relation of the specific refractory power of film.
Claims (5)
1, the yttrium oxide constituent used of a kind of evaporation is characterized in that containing titanium oxide and zirconium white.
2, a kind of evaporation as claimed in claim 1 yttrium oxide constituent, the content that it is characterized in that titanium oxide is 0～7.3% weight, zirconic content is 0～90% weight.
3, a kind of evaporation as claimed in claim 1 or 2 yttrium oxide constituent is characterized in that it being to sinter the tablet shape into after yttrium oxide, titanium oxide and zirconium white are mixed.
4, a kind of manufacture method of antireflection film is characterized in that using the film that contains titanium oxide and the group of zirconic evaporation usefulness yttrium oxide constituent manufacturing as silicon or Ga As.
5, a kind of manufacture method of antireflection film as claimed in claim 4 is characterized in that with electron beam gun heated oxide yttrium composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62023946A JPS63192856A (en) | 1987-02-04 | 1987-02-04 | Production of yttrium oxide composition for vapor deposition and antireflection film |
| JP23946/87 | 1987-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87107819A true CN87107819A (en) | 1988-08-17 |
| CN1017164B CN1017164B (en) | 1992-06-24 |
Family
ID=12124709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107819A Expired CN1017164B (en) | 1987-02-04 | 1987-11-12 | Preparation of antireflection coating on silicon or galliumarsenide substrate |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS63192856A (en) |
| KR (1) | KR910008716B1 (en) |
| CN (1) | CN1017164B (en) |
| DE (2) | DE3890060C2 (en) |
| SE (1) | SE8803506D0 (en) |
| WO (1) | WO1988005963A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2850371B2 (en) * | 1989-06-19 | 1999-01-27 | 松下電器産業株式会社 | Image output device |
| CN102140621A (en) * | 2011-03-10 | 2011-08-03 | 苏州大学 | Preparation method of dense composite titanium dioxide film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246043A (en) * | 1979-12-03 | 1981-01-20 | Solarex Corporation | Yttrium oxide antireflective coating for solar cells |
| DE3613501A1 (en) * | 1986-04-22 | 1987-10-29 | Stefan Dipl Ing Donnerhack | Process for anti-catalytic coating of thermocouples |
-
1987
- 1987-02-04 JP JP62023946A patent/JPS63192856A/en active Pending
- 1987-11-12 CN CN87107819A patent/CN1017164B/en not_active Expired
-
1988
- 1988-02-04 WO PCT/JP1988/000103 patent/WO1988005963A1/en active Application Filing
- 1988-02-04 KR KR1019880701199A patent/KR910008716B1/en not_active IP Right Cessation
- 1988-02-04 DE DE19883890060 patent/DE3890060C2/en not_active Expired - Lifetime
- 1988-02-04 DE DE19883890060 patent/DE3890060T/de active Pending
- 1988-10-03 SE SE8803506A patent/SE8803506D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3890060C2 (en) | 1990-08-16 |
| KR910008716B1 (en) | 1991-10-19 |
| CN1017164B (en) | 1992-06-24 |
| SE8803506L (en) | 1988-10-03 |
| DE3890060T (en) | 1989-03-23 |
| JPS63192856A (en) | 1988-08-10 |
| SE8803506D0 (en) | 1988-10-03 |
| KR890700927A (en) | 1989-04-28 |
| WO1988005963A1 (en) | 1988-08-11 |
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