CN1333293C - Substrate with diaphragm using silver alloy film for reflective electrode - Google Patents
Substrate with diaphragm using silver alloy film for reflective electrode Download PDFInfo
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- CN1333293C CN1333293C CNB03159882XA CN03159882A CN1333293C CN 1333293 C CN1333293 C CN 1333293C CN B03159882X A CNB03159882X A CN B03159882XA CN 03159882 A CN03159882 A CN 03159882A CN 1333293 C CN1333293 C CN 1333293C
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Abstract
On a substrate, a substrate film, such as ITO growing the silver alloy with the stable crystal, is formed and the stable growth of silver crystal is generated regardless of kind of the silver alloy by forming the silver alloy-base thin film on the above film. As a result, the silver electrode obtains the high durability to the stable crystal regardless of the components of this alloy and at the same time, the stabilities of reflecting characteristics and etching characteristics are realized.
Description
Technical field
The present invention relates to a kind of reflecting electrode type liquid crystal display, particularly be used for the substrate that reflecting electrode is used film of having of this liquid crystal display.
Background technology
As the display device of liquid crystal indicator or EL (electroluminescence) display device etc., employing need not be carried on the back the display device of the reflection-type of irradiation.
In the display device of reflection-type, adopt reflective electrode substrate.In addition, reflective electrode substrate also is used to solar cell etc.
Starting material as above-mentioned reflecting electrode adopt aluminium more, but have proposed to adopt the motion of permanance than aluminium silver high, that light reflectivity is high.Look-ahead technique as adopting silver as the reflective electrode material describes with regard to following two inventions.
Open in the flat 11-44887 communique the spy, as display device reflective electrode substrate with high-performance (high reflectance) and high reliability, disclose by add from platinum, palladium, gold, nickel, copper, select more than one metal the thin mould of silver alloy and and substrate between the reflecting electrode that constitutes of the such double-decker of the knitting layer that sets.
This electrode is by adopting alloy system based on silver as reflecting electrode, corrosive high reflectance that keeps simultaneously can suppressed, in addition, the metal that is used for alloy uses the work function metal higher than silver, scope is below 5at%, by adopting at knitting layer with indium oxide or tin oxide is the electric conductivity pottery (ITO) of the mixed oxide formation of base material, can improve the substrate adaptation, prevents broken string.
In addition, open in the flat 7-134300 communique the spy, but as the silver clear display picture, that be difficult for to produce display defect, reflection-type liquid-crystal display device that reliability is good is reflecting electrode, reported by adding metal than silver-colored easy oxidation, the silver-colored aggegation that causes because of heat can be prevented, the electrode of high-durability can be obtained.In this invention, by in silver, adding the metal of from magnesium, aluminium, titanium, zirconium, hafnium, selecting more than a kind or 2 kinds, can prevent the thermal oxide of silver, keep the reflecting electrode performance.
Problem points as the conventional art of above-mentioned communique record has the problem that reduces silver-colored distinctive high light reflectivity performance by alloying silver.By alloying silver, improved silver-colored permanance, and its permanance depends on the addition of the metal that becomes alloy.Yet, in order to improve the permanance of silver, as improve the addition of other metals, can destroy the crystallinity of silver, reduce reflectivity.In addition, as guaranteeing the highly reflective of silver electrode, just must suppress the addition of other used metals of its alloying, consequently the permanance of silver electrode reduces.
In addition, the metal that above-mentioned alloying is used as increasing addition for improving permanance, can significantly increase cost owing to be high price metals such as palladium or platinum.
In addition, as adopting alloy silver electrode, because the grain boundary of silver changes according to additive, produce the corrosive inequality because of the uneven alloy silver electrode that causes of additive, the result makes the unsettled danger of electrode processing dimension.
Therefore, problem of the present invention is, makes stable silver-colored crystallization by disobeying the used metal of alloying with the ratio (ratio of silver alloy) of silver, obtains having the display body of all high silver electrode of permanance and reflectivity.
In addition, problem of the present invention is, even provide a kind of ratio with minimizing silver alloy also to have the display body of the film of silver electrode cheaply of high-durability.
In addition, problem of the present invention is that the stable crystal grain by the ratio making of disobeying silver alloy has permanance obtains having the display body that can obtain to stablize corrosive silver electrode.
Summary of the invention
Utilize following formation to solve the problem of the invention described above.
That is, with the reflecting electrode film substrate that adopts silver alloy film, forming the substrate film with the crystalline growth of stablizing silver alloy on substrate, is film by forming silver alloy in the above, disobeys the silver alloy kind, produces the stable growth of silver-colored crystallization.As a result, under the situation that does not change its alloy composition, obtain to realize the stabilization of reflecting properties and corrosive nature in the high-durability of stable crystalline.This film preferably has following feature:
1. the composite oxides of above-mentioned substrate film for constituting by indium oxide and tin oxide.
2. film is characterized in that: the crystallinity of the substrate film that is made of indium oxide and tin oxide is by (222)/(400) orientation ratio, more than 1.0.
3. film is characterized in that: the average crystal grain boundary diameter of the substrate oxide film that is made of indium oxide and tin oxide is 100nm～200nm.
4. film is characterized in that: the ratio resistance of the substrate oxide film that is made of indium oxide and tin oxide is 100～300 μ Ω cm.
5. above-mentioned silver alloy is the alloy that contains more than one elements in palladium, platinum, gold, copper, indium, tin, zinc, the samarium (Sm) etc.
6. film, it is characterized in that: the ratio of components of the silver in the silver alloy is more than 97 weight %.
The present invention is conceived to the invention that the repeatability of the stability of the crystallization of silver alloy and grain boundary is finished, and below explanation obtains the reason of this silver alloy film character.
1. the stabilization of the crystallization of silver alloy film
The reflective electrode film that is used for the silver alloy system of crystallization display body is characterized in that reflecting properties compares special height with in the past aluminium and aluminium alloy system.This feature is the feature of silver itself, though the reflectivity of fine silver film is best, owing to itself have agglutinophilic characteristic, so have when crystallization is insufficient the significantly reduced feature of permanance.
In addition, why can improve permanance by making metalized ag, even be because crystallization is insufficient, but owing to when contacting with the material that makes aggegations such as water and oxygen, can capture this material than the atom of the easy oxidation of silver, so can prevent the deterioration of silver.
But its reflectivity changes because of the metal beyond the silver contained in the silver alloy, and generally speaking, content highly reflective more reduces more.This is because the reflectivity that silver itself has is subjected to micro-additive, is the obstruction of other metals.That is, owing to producing silver-colored crystallization for demolishing other metallic atoms, its form depends on the formation of (1) lattice imperfection and (2) grain boundary.
Therefore, for the few silver alloy of additive that makes approximate silver-colored self character is also kept high permanance, the inventor finds out the following method that makes silver-colored noncrystalline portion do one's utmost to reduce.
That is,, make the membranous selection of this substrate film meet the material of the condition of the crystalline growth that promotes silver, reduce the noncrystalline part of silver alloy, increase crystalline portion by substrate film is set on substrate.
Above-mentioned substrate film adopts the composite oxides (ITO) of indium oxide and tin oxide, and by controlling the crystallinity of this ITO film, control silver is the crystallinity of alloy.
By within a cube crystalline substance, Michaelis symbol (222) face and (400) face, increasing crystalline texture (111) face and approaching (222) face of grating constant of silver, realize that silver is the crystalline scope of alloy.
The ratio of (222) face of being somebody's turn to do is preferably by (222)/(400) ratio, more than 1.0.Above-mentioned (222) even the above-mentioned ratio of face is lower than 1.0 values, with on substrate directly film forming compare also and can expect crystallization, but its effect is insufficient.
In addition, except that the above-mentioned ratio of crystal plane, the crystallinity of substrate film is also very important, certainly, does not wish the sufficient crystallising of silver on amorphous ITO film.Therefore, one of index of silver-colored crystallization than resistance preferably near 100 μ Ω cm of the theoretical value of ITO in the scope of the 300 μ Ω cm that can expect sufficient crystallising.
2. the control of grain boundary
For the above reasons, (222) face of faces substrate film ITO, the crystallization-stable growth of silver.Therefore, the shape of Yin grain boundary is subjected to the influence of the shape of substrate film ITO.
In addition, the reflecting electrode of crystallization display body, owing to need process by corrosion treatment, so corrosivity also becomes important function.Corrosion is owing to carrying out along the grain boundary, so the form of grain boundary and homogeneity are directly connected to the homogeneity of corrosion.Therefore, in order to corrode the display body front equably, make the grain boundary of silver of whole of substrate even also very important.
Therefore, by when controlling the crystallinity of substrate film ITO, also adjust the grain boundary of ITO, the particle diameter of the grain boundary of control silver alloy film can make the corrosivity homogenising.
The size of this grain boundary is preferably pressed the mean grain size of the major diameter and the minor axis on average crystal grain border, in the scope of 100nm～200nm (Fig. 1).As in the scope of 100nm～200nm, can improve the reflectivity of short wavelength side.If the grain boundary is oversize, the fluctuating on silverskin surface increases, and the result because it is at random to produce the light of short wavelength side, produces corrosion miniaturization, homogenising and improvement reflection characteristic and carries out synchronously.
Mean grain size is as surpassing 200nm, and corrosion forms heterogeneity (Fig. 2) easily, and in addition, mean grain size reduces the situation that the crystallinity of substrate film reduces and increases under the situation below the 100nm, and in such cases, permanance goes wrong, so not preferred (Fig. 3).
By controlling SiO on one side
2The total gas flow of oxygen concentration and ITO Yi Bian carry out film forming, can be controlled at 100nm～200nm with the ITO particle size.In addition, as becoming the ITO film under these conditions, also can form than the film of resistance at 100～300 μ Ω cm.
In addition, when the ratio of components of silver is lower than 97 weight %, the collapse of the crystallinity of silver, reflecting properties reduces.So, keep good reflection characteristic, must be more than 97 weight %.
In Fig. 1 (Fig. 1 (a) is an outboard profile, and Fig. 1 (b) is a planimetric map), pattern shows that crystallinity is good, the silver alloy film (spot part) that the grain boundary is little and (222) substrate film (white background film) many, that the grain boundary is little.Hereinto under the situation, (222) grating constant of substrate ITO is about 9.9 dusts, and grating constant of (111) silver is about 4.1 dusts, because grating constant of (111) silver is joined by about 1/2 of the grating constant of (222) substrate ITO, therefore the silver easy crystallization that becomes can improve the permanance of silver alloy.In addition, because the grain boundary is little, the corrosion pattern processability improves.
In Fig. 2 (Fig. 2 (a) is an outboard profile, and Fig. 2 (b) is a planimetric map), the substrate film (white background film) that silver alloy film (spot portion) that the modal representation grain boundary is big and grain boundary are big.Hereinto under the situation, the well-crystallized, the permanance height, still, because the grain boundary increases the corrosion pattern poor in processability.
In Fig. 3 (Fig. 3 (a) is an outboard profile, and Fig. 3 (b) is a planimetric map), modal representation does not carry out the silver alloy film (spot portion) of crystallization and does not carry out the substrate film (white background film) of crystallization.Under the situation, crystallization is poor hereinto, is easy to generate the aggegation of noncrystalline portion, and permanance is low.In addition, the pattern processability is also poor.
Display body of the present invention as the reflecting electrode type liquid crystal display or the EL display body of colored STN type, can be used as the display body of the reflection-type of not using back of the body irradiation.In addition, reflective electrode substrate also can be used for solar cell etc.
Description of drawings
Fig. 1 is outboard profile (Fig. 1 (a)) and the planimetric map (Fig. 1 (b)) that modal representation has the substrate of the little substrate film in the little silver alloy film in the grain boundary of alloy silver electrode of the present invention and grain boundary.
Fig. 2 is outboard profile (Fig. 2 (a)) and the planimetric map (Fig. 2 (b)) that modal representation has the substrate of the big substrate film in the big silver alloy film in grain boundary and grain boundary.
Fig. 3 is outboard profile (Fig. 3 (a)) and the planimetric map (Fig. 3 (b)) that modal representation has the substrate of alloy silver electrode that does not carry out crystallization and the substrate film that does not carry out crystallization.
Embodiment
Below, embodiments of the present invention are described.
On glass substrate, form the ITO film with sputter equipment, form in the above 2 kinds of silver alloy (Ag: Pd=99.5: 0.5 weight %) and (Ag: Pd=99: film 1 weight %), measure its reflection characteristic and heat-resisting after reflection characteristic.In addition, by the fixing condition of end liner ITO of the formation of above-mentioned film, change the membrance casting condition of silver alloy in addition, evaluation corrosivity.All conditions below are shown.
Substrate: soda-lime glass thickness of slab 0.5t
Substrate film: ITO (using sputtering film-forming)
Thickness 120nm
The integrated intensity of crystallinity (222)/(400) is than 210.9 ÷ 95.1=2.218
Than resistance 160 μ Ω cm
Mean grain size 143nm
Silver alloy: Ag/Pd (using sputtering film-forming)
Thickness 200nm
Pressure 0.6Pa
220 ℃ of temperature
Reflectivity when placing 1 hour under the ambiance when the initial stage reflectivity of the silver alloy film that obtains and 250 ℃ is shown in table 1.
Table 1
| Ag: Pd ratio of components | Wavelength | Initial stage reflection % | Heat-resisting reflection % (250 ℃ of 1h) |
| 99.5: 0.5 weight % | 400nm | 90.7 | 77.6 |
| 550nm | 96.3 | 92.4 | |
| 700nm | 97.8 | 97.3 | |
| 99: 1 weight % | 400nm | 88.2 | 77.3 |
| 550nm | 95.3 | 91.4 | |
| 700nm | 97.7 | 96.7 |
Although the addition difference of the palladium from the silver alloy that above-mentioned table 1 obtains, the basic indifference of heat-resisting reflectivity (thermotolerance).Therefore show, even the ratio of silver alloy, also can obtain sufficient permanance (anti-compendency) near fine silver.
In addition, be to understand the corrosivity of gained silver alloy, with pressure, temperature, 3 parameters of discharge power be standard adjust the AgPd alloy (Ag: Pd=99.5: sputtering condition 0.5 weight %), measured etching time.It the results are shown in table 2.
Under all conditions, thin and thick all is 200 ± 10nm.
Table 2
| Ag: Pd ratio of components | Substrate ITO etching condition nitric acid 0.85 with above-mentioned characteristic: phosphoric acid 63.2: 23 ± 3 ℃ of acetic acid 33 weight % | ||
| 99.5: 0.5 weight % | |||
| Pressure Pa | Temperature ℃ | Discharge output power Kw | Etching time sec |
| 0.3 | 150 | 2 | 45 |
| 0.3 | 150 | 3 | 45 |
| 0.3 | 150 | 6 | 45 |
| 0.3 | 180 | 2 | 45 |
| 0.3 | 180 | 3 | 45 |
| 0.3 | 180 | 6 | 45 |
| 0.3 | 220 | 2 | 45 |
| 0.3 | 220 | 3 | 45 |
| 0.3 | 220 | 6 | 45 |
| 0.6 | 150 | 2 | 45 |
| 0.6 | 150 | 3 | 45 |
| 0.6 | 150 | 6 | 45 |
| 0.6 | 180 | 2 | 45 |
| 0.6 | 180 | 3 | 45 |
| 0.6 | 180 | 6 | 45 |
| 0.6 | 220 | 2 | 45 |
| 0.6 | 220 | 3 | 45 |
| 0.6 | 220 | 6 | 45 |
| 0.9 | 150 | 2 | 45 |
| 0.9 | 150 | 3 | 45 |
| 0.9 | 150 | 6 | 45 |
| 0.9 | 180 | 2 | 45 |
| 0.9 | 180 | 3 | 45 |
| 0.9 | 180 | 6 | 45 |
| 0.9 | 220 | 2 | 45 |
| 0.9 | 220 | 3 | 45 |
| 0.9 | 220 | 6 | 45 |
No matter the etching condition that draws silver alloy film from above-mentioned table 2 how, corrosivity is all even.By promoting the crystallization of silver, can seek to prevent condensing of silver, improve the permanance of alloy silver electrode.
In addition, even do not increase the ratio of alloy,, can obtain the alloy silver electrode of reflectivity near the high reflectance of silver owing to can improve permanance.
Particle diameter by the control grain boundary reaches evenly the corrosivity of silver-colored grain boundary, improves its processability.In addition, by the miniaturization of grain boundary, also improve the reflectivity of short wavelength side.
Owing to not needing to add a large amount of high-valency metals, so can access alloy silver electrode cheaply for improving permanance.
Claims (4)
1. with the substrate of the reflecting electrode that adopts silver alloy film with film, it is characterized in that: the substrate film that on substrate, forms the composite oxides that constitute by indium oxide and tin oxide, forming silver alloy in the above is film, and the average crystal grain border of the substrate film that is made of indium oxide and tin oxide directly is 100nm～200nm.
As claim 1 record with the substrate of the reflecting electrode that adopts silver alloy film with film, it is characterized in that: the ratio resistance of the substrate oxide film that is made of indium oxide and tin oxide is 100～300 μ Ω cm.
3. use the substrate of film as the reflecting electrode with the employing silver alloy film of claim 1 or 2 records, it is characterized in that: silver alloy is the alloy that contains more than one elements in palladium, platinum, gold, copper, indium, tin, zinc, the samarium (Sm).
4. use the substrate of film as the reflecting electrode of claim 1 or the 2 employing silver alloy films of putting down in writing, it is characterized in that: the ratio of components of the silver in the silver alloy is more than 97 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP292365/2002 | 2002-10-04 | ||
| JP2002292365A JP2004124209A (en) | 2002-10-04 | 2002-10-04 | Substrate with thin film for reflecting electrode using silver alloy film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493906A CN1493906A (en) | 2004-05-05 |
| CN1333293C true CN1333293C (en) | 2007-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03159882XA Expired - Fee Related CN1333293C (en) | 2002-10-04 | 2003-09-26 | Substrate with diaphragm using silver alloy film for reflective electrode |
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| Country | Link |
|---|---|
| JP (1) | JP2004124209A (en) |
| CN (1) | CN1333293C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6825218B2 (en) * | 2016-03-30 | 2021-02-03 | 大日本印刷株式会社 | Parallax barrier member |
| CN109971382B (en) * | 2019-04-29 | 2023-12-29 | 九江力达科技股份有限公司 | Energy-saving cooling heat-insulating car cover film and preparation method thereof |
| CN112635691B (en) * | 2020-12-31 | 2022-07-12 | Tcl华星光电技术有限公司 | Array substrate and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09304787A (en) * | 1996-05-14 | 1997-11-28 | Toppan Printing Co Ltd | Electrode substrate for display device |
| JPH10282906A (en) * | 1997-04-10 | 1998-10-23 | Toppan Printing Co Ltd | Electrode substrate for display device |
| JPH1144887A (en) * | 1997-07-28 | 1999-02-16 | Toppan Printing Co Ltd | Reflection electrode substrate for display device |
-
2002
- 2002-10-04 JP JP2002292365A patent/JP2004124209A/en active Pending
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2003
- 2003-09-26 CN CNB03159882XA patent/CN1333293C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09304787A (en) * | 1996-05-14 | 1997-11-28 | Toppan Printing Co Ltd | Electrode substrate for display device |
| JPH10282906A (en) * | 1997-04-10 | 1998-10-23 | Toppan Printing Co Ltd | Electrode substrate for display device |
| JPH1144887A (en) * | 1997-07-28 | 1999-02-16 | Toppan Printing Co Ltd | Reflection electrode substrate for display device |
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| Publication number | Publication date |
|---|---|
| JP2004124209A (en) | 2004-04-22 |
| CN1493906A (en) | 2004-05-05 |
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