CN100491583C - Base plate with ITO transparent conductive film and method for preparing same - Google Patents
Base plate with ITO transparent conductive film and method for preparing same Download PDFInfo
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- CN100491583C CN100491583C CNB2005100488995A CN200510048899A CN100491583C CN 100491583 C CN100491583 C CN 100491583C CN B2005100488995 A CNB2005100488995 A CN B2005100488995A CN 200510048899 A CN200510048899 A CN 200510048899A CN 100491583 C CN100491583 C CN 100491583C
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- 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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- 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
- C23C14/02—Pretreatment of the material to be coated
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/541—Heating or cooling of the substrates
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
To provide a method for depositing an ITO transparent conductive film on a substrate having organic polymers. The ITO transparent conductive film deposition method by an ion-plating apparatus employing a pressure gradient type plasma gun installed in a vacuum chamber is provided, wherein an ITO transparent conductive film is deposited while the temperature of the substrate before the film deposition is set to be 80-145[deg.]C, and radiation heat incident on the substrate per unit area and a unit time from an ITO evaporation raw material is set in the range of 1.5-10 J/cm<SP>2</SP>*min. The pressure in the vacuum chamber is set to be 0.05-0.3 Pa. In the ITO transparent conductive film, tin of 5-10 wt.% is added to indium oxide in terms of oxide, and the specific resistance is in the range of 1.2*10<SP>-4</SP>and 3.0*10<SP>-4</SP>[Omega]cm.
Description
The present invention relates to a kind of method that is used for forming the ITO nesa coating on substrate, it is used for flat-panel monitor, electronics, solar cell, optical device or the like.Particularly, it relates to a kind of being used in the method that comprises formation ITO nesa coating on the substrate of organic polymer films.
Nesa coating is a kind of basic, important element in flat-panel monitor and solar cell, because of it has the peculiar property of printing opacity and conduction.
In many cases, the ITO nesa coating forms by the vacuum film formation method.The example of the vacuum film formation method of this ITO of being used to form nesa coating is ion plating, sputtering method and vapor deposition.Certainly sputtering method is to use the most widely.
The ITO nesa coating is relevant with forming by sputtering method, and JP-A-9-171188 discloses a kind of method, wherein by under 300 ℃ or higher temperature to the substrate heating, acquisition has 2 * 10
-4The low-resistance ITO nesa coating of Ω cm.
JP-A-9-25575 and JP-A-2000-17430 disclose ion plating by utilizing pressure gradient type plasma gun, and heating obtains the ITO nesa coating to substrate under about 200 ℃ lesser temps.
In indicating meter and electronic device field,, thin thickness in light weight and have more flexible equipment in order to make, have and propose to replace conventional inorganic substrate (for example glass) with such substrate, wherein organic membrane is clipped between a plurality of inorganic substrates, perhaps by a kind of organic substrate made that is selected from the various polymkeric substance.Today, it is complicated that device structure becomes.In some cases, there is machine equipment to be formed on the inorganic substrate, for example the LCD colour filter.
State in the use in the situation of organic polymer substrate or the above-mentioned substrate that comprises organic substance, it is formed at the surface of inorganic substance or the inside of inorganic substance, and this substrate thermotolerance is poor with respect to the substrate of being made by inorganic materials (for example glass).Thereby this substrate may be out of shape or may have problems, and wherein their machinery and electrical properties (for example Young's modulus, specific refractory power, scattering coefficient and specific inductivity) change obviously when substrate is heated near their melting temperature.
Therefore, have the substrate of organic polymer, be necessary temperature is reduced to 200 ℃ or lower for use.Since this point, the resistance of ITO nesa coating when being difficult to reduce by spatter film forming.
Known ion plating by employing pressure gradient type plasma gun can produce the low resistance film, even the temperature of substrate is lower.Yet, during making the ITO nesa coating, because from the high-density plasma bundle of pressure gradient type plasma gun with from the radiant heat of ITO evaporation source, substrate temperature increases sharply.In order to prevent that this temperature from increasing, and can increase the transfer rate (referring to JP-A-1-313810) of substrate.For this situation, the ITO nesa coating that must have very fast film forming speed manufacturing to have to want thickness.Therefore, the situation for the plasma gun of applying pressure gradient type must increase the power that puts between negative electrode and the anode.Because this, the heat that is radiated substrate increases because of the high-density plasma bundle with from the radiation of ITO evaporation source.Thereby the substrate temperature between film stage may rapidly increase to the temperature near the organic polymer fusing point.This may cause the distortion to the initial configuration of substrate.In addition, for example, from substrate, may produce decomposition gas.This may greatly reduce the electroconductibility of ITO nesa coating.
Summary of the invention
Therefore, the purpose of this invention is to provide and a kind ofly have on the substrate of organic polymer the method that effectively forms indium tin oxide (ITO) nesa coating.
According to the present invention, provide a kind of and on substrate, formed the method for ITO nesa coating by the ion plating device, comprise step:
(a) in vacuum chamber, produce beam-plasma from pressure gradient type plasma gun;
(b) with these ion beam irradiations ITO source, with heating and evaporate this ITO source;
(c) make the ITO source ionization of evaporation by plasma atmosphere; And
(d) this Ionized ITO source of deposition on substrate, with formation ITO nesa coating on this substrate,
This method feature is, adjusts to 1.5-10.0J/cm during the step (d) temperature of substrate being adjusted to 80-145 ℃ and the radiant heat that during step (d) time per unit and per unit area incided substrate from the ITO source at least at least
2Min.
According to the present invention, form the ITO nesa coating that obtains by aforesaid method and comprise the Indium sesquioxide that is mixed with tin, condition is that tin is oxide form, the weight part of tin accounts for 5-10wt%, and has from 1.2 * 10
-4To 3.0 * 10
-4The resistivity of Ω cm.
Description of drawings
Fig. 1 is the synoptic diagram that the film deposition system of the ion plating (activating reaction deposition) that has been used to adopt pressure gradient type plasma gun is shown;
Fig. 2 is the synoptic diagram that another film deposition system of the ion plating (activating reaction deposition) that has been used to adopt pressure gradient type plasma gun is shown;
Fig. 3 is an amplification profile diagram, and it is illustrated in the ITO nesa coating that forms on the substrate of being made by organic polymer etc.
Embodiment
Film forming shown in Figure 1 can be used for implementing aforesaid method of the present invention with the ion plating device.This device has vacuum chamber 1, be connected to the pressure gradient type plasma gun 2 of vacuum chamber 1 sidewall, be arranged on vacuum chamber 1 bottom crucible 3, be arranged on the substrate holder 4 and the vacuum-pumping equipment 17 of the top area of vacuum chamber 1.
The inner face of crucible 3 is put into ITO source (for example ITO particle) 19.This ITO (indium tin oxide target) can be determined by the zinc oxide that is mixed with tin.Suppose that it is 100wt% that tin is taked the form of oxide compound and the gross weight of ITO, this tin can account for the weight part of 5-10wt% so.Be provided with a permanent magnet 22 that is used for deviation and focuses on beam-plasma 12 in the bottom of crucible 3.In addition, vacuum-pumping equipment 17 is connected to vacuum chamber 1 by conduction valve (conductance valve) 16, so that vacuum chamber 1 is bled.In the present invention, preferably,,, make conductance valve 16 have certain opening, thereby the pressure adjustment of vacuum chamber 1 is led in the scope of 0.05-0.3Pa by adjusting suction performance based on the measured value of the vacuumometer 18 that is connected to vacuum chamber 1.
In order to keep the pressure of vacuum chamber 1, the pressure lower than 0.05Pa is disadvantageous economically, because it may cause the extraction equipment load too big, and owing to makes vacuum chamber 1 have unnecessary charge capacity.If the pressure in the vacuum chamber surpasses 0.3Pa in step (d), before the ITO source of evaporation arrived substrate, the ITO source of evaporation just collided too many argon molecules and oxygen molecule so.Because this, the ITO source of evaporation has discharged energy basically.This may greatly reduce the electroconductibility of the ITO nesa coating that is deposited on the substrate 25.Therefore, at least during step (d), preferably in step (b), (c) with (d), this pressure is preferably 0.3Pa or lower, more preferably 0.15Pa or lower.
Pressure gradient type plasma gun 2 is furnished with the cylindrical tube 9 of one end by negative electrode 8 sealings.The right cylinder of being made by molybdenum 7 is fixed to negative electrode 8.Right cylinder 7 has the conduit of being made by titanium (Ta) 5 in its axle center, portion's one end has the disk of being made by LaB6 6 within it.These conduits 5 and disk 6 are built in the right cylinder 7.Negative electrode 8 links to each other with the negative pole of the power supply 10 that is used to discharge.Crucible 3 in vacuum chamber 1 bottom links to each other with the positive pole of power supply 10, and constitutes anode.In the formation of ITO nesa coating, argon gas 20 is introduced conduit 5, between the negative electrode 8 of pressure gradient type plasma gun and the crucible 3 (anode) in the vacuum chamber 1, produce discharge then, thereby form beam-plasma 12.
By being used for the ring focusing coil 21 of the cross-sectional constriction of beam-plasma 12 and being used for beam-plasma 12 deviations and focusing on the permanent magnet in ITO source 19, formed beam-plasma 12 focuses on the ITO source 19 of crucible 3, heats thus and evaporates ITO source 19.
As shown in Figure 1, substrate holder 4 is rotated by the motor (not shown).Above substrate holder 4, provide a well heater 11 and a thermometer 13 that is used for heated substrates 25.Well heater 11 is to be used for keeping substrate 25 to be in predetermined temperature (for example 80-145 ℃).Thereby based on the measured temperature of thermometer 13, the output of well heater 11 is controlled.Well heater 11 can be a lamp well heater, for example tungsten sodium lamp (tungsten halogen lamp), xenon arc lamp and graphite heater.
For substrate 25 being heated to a predetermined temperature, can before forming film, make calibration curve, for example, description below.In the step (a) of method before, substrate 25 is through preheating.During preheating, measure the temperature (actual temperature) of substrate 25 with the provisional interim thermometer (for example hot coupling meter) that is connected on the substrate 25.With this measurement synchronization, also with being arranged on the approximate temperature of measuring substrate 25 near the thermometer 13 of substrate 25.Then, from reality with proximate temperature produce calibration curve.After that, take interim thermometer away from substrate 25.Calibration curve provides actual temperature from approximate temperature.At least during step (d), only measure approximate temperature by thermometer 13, and determine the temperature of substrate from calibration curve, it is as the estimated value of actual temperature, and adjusts to 80-145 ℃ by the output of control heater 11.
Sidewall at vacuum chamber 1 is equipped with oxygen introducing nozzle 14.As required, utilize the mass flow controller (not shown) to be fed in the vacuum chamber 1 by these nozzle 14 oxygen 15.
Pressure gradient type plasma gun 2 has a structure, it remains on the level of a pressure that is higher than vacuum chamber 1 by the internal pressure with plasma gun 2 and by filling the inside of plasma gun 2 with argon gas always always, thereby prevents the deterioration that causes because of oxygen 15.Therefore, can prevent that oxygen 15 oxidations and deterioration are exposed to the conduit 5 (being made by Ta) of the plasma gun 2 under the high temperature and disk 6 (by LaB
6Make).
As can be seen from Fig. 3, by adopting the ion plating device of Fig. 1, can form ITO nesa coating 24 on the surface of substrate 25.Substrate 25 can wholely be made or can be made as the matrix material of submember as basal component and organic polymer by comprising inorganic materials by organic polymer.
Top organic polymer is not special the qualification.Its example comprises polymer plastic resin for example polyethylene terephthalate, polycarbonate, polymethylmethacrylate, PEN, polyethersulfone, nylon, polypropylene ester (polyalylate), cycloolefine polymer.Can use these organic polymers as substrate 25 with the form of alignment films or fuel plate.
Corona discharge Treatment can be passed through in the surface that constitutes the organic polymer of substrate 25, and the grappling coating is handled, perhaps smoothing processing.
The other example of substrate 25 comprises, a film or airbond film (for example a, SiO who wherein forms inorganic materials on organic polymer
2, SiO
x, SiON, SiN, SiOCN and SiAlON) substrate, an inorganic materials (glass wherein, pottery or metal) be coated with the substrate of heat labile organic substance, perhaps a substrate that wherein on primary element, forms electronics (for example, organic EL (electroluminescent) equipment).
The ITO nesa coating that forms on substrate 25 can be determined by the Indium sesquioxide alkene that mixes.Suppose that it is 100wt% that tin is taked the form of oxide compound and the gross weight of ITO film, this tin can account for the weight part of 5-10wt%.In other words, Indium sesquioxide and be 100wt% with the gross weight of the tin of oxide form.
If the weight part of tin (stannic oxide form) is less than 5wt%,, the carrier concentration of ITO nesa coating may become too low so.If it surpasses 10wt%, carrier mobility may become too low so.In both cases, the electric conductivity of ITO film may become too little.Thereby it is preferably 5-10wt%.
An illustrative steps utilizing the film deposition system of Fig. 1 to form ITO nesa coating 24 on substrate 25 is explained as follows.
The crucible of being made by carbon 3 is equipped with ITO source 19.The crucible 3 of charging is placed on the bottom of vacuum chamber 1.ITO source 19 is particle form preferably, but its form is not particularly limited.
The substrate 25 that is used for forming the ITO nesa coating thereon is connected to substrate holder 4, then vacuum chamber 1 is evacuated to about 2 * 10
-4The pressure of Pa.In view of the above, substrate is heated to preset temperature, to remove gas that substrate 25 surfaces are absorbed and from substrate 25 inner escaping gas.
After bleeding, by the functional quality flow director argon gas stream speed is adjusted to 10-40 standard cubic centimeter per minute (sccm) (not shown) and argon gas 20 is fed to vacuum chamber 1 through pressure gradient type plasma gun 2.
Then, by oxygen supply nozzle 14 oxygen 15 is fed to vacuum chamber 1.In order stably to implement film forming, at least during step (d), be preferably in step (b), (c) and (d) during, by adjusting suction performance, the pressure in the vacuum chamber 1 is adjusted to the scope of 0.05-0.3Pa with the opening that is arranged on the conductance valve 16 between vacuum-pumping equipment 17 and the vacuum chamber 1.
Based on the pressure in the output of film forming speed, pressure gradient type plasma gun, the vacuum chamber 1 and the temperature of substrate 25, the flow velocity of oxygen 15 is set to optimum value.
Then, give pressure gradient type plasma gun 2 energisings, make it to produce beam-plasma 12.The beam-plasma 12 that obtains is focused on ITO source 19 in the crucible 3 by focusing coil 21 and permanent magnet 22, thus ITO source 19 is heated to the temperature of ITO source 19 evaporations.Then, the oxygen 15 of the ITO source of evaporation and introducing is in plasma atmosphere 23 intermediate ionizations.Then, by the opening (not shown) that is installed in the flashboard below the substrate 25 Ionized ITO source is deposited on the substrate 25.
Under the potential difference effect between the floating potential of the plasma potential of the plasma body in this atmosphere and substrate 25, quicken to substrate 25 in Ionized ITO source.Thereby the ionization ITO source with macro-energy of about 20eV arrives and is deposited on the basal surface of substrate 25, forms the ITO nesa coating of low resistance, densification thus.
If the temperature of substrate 25 is lower than 50 ℃ during the step (d) of this method, the ITO electrically conducting transparent membrane resistance that obtains so becomes too high.This ITO film is difficult to use in the equipment.
If substrate 25 is heated to about 80 ℃, ITO nesa coating 24 can reduce resistance so, and improves electric conductivity thus.Therefore, during step (d), preferably substrate 25 is heated to 80 ℃ or higher temperature.If the temperature by well heater 11 substrates 25 is set to be higher than 145 ℃, because of Ionized ITO source stacked on substrate 25 and because of the radiant heat in ITO source, it may be above 200 ℃ subsequently so.Therefore, preferably the temperature of substrate 25 is adjusted to 145 ℃ or lower.
Form on the substrate 25 ITO nesa coating 24 during because from the radiant heat in high-density plasma bundle 12 and ITO source 19, the temperature of substrate 25 is easy to increase sharply.In order to prevent the quick increase of this temperature, the heat (radiant heat) that preferably will be radiated on the substrate 25 is adjusted to 10.0J/cm
2Min or lower for example, is applied to negative electrode 8 and crucible 3 (anode) by control and goes up with the power to the power supply 10 of pressure gradient type plasma gun 2 energisings.In order to form the outstanding ITO nesa coating of electroconductibility, preferably heat (radiant heat) is adjusted to 1.5J/cm
2Min or higher.
Usually, perhaps be installed in the suction performance of the extraction equipment on the vacuum chamber, perhaps introduce the amount (speed) of the gas of vacuum chamber, can adjust the pressure in the vacuum chamber by control by control.Yet in the present invention, the former (also being suction performance control) is better than the latter (also promptly cause and introduce rate-controlling), will explain below.
If the suction performance that is installed in the vacuum-pumping equipment 17 on the vacuum chamber 1 by control is adjusted the pressure in the vacuum chamber 1, oxygen partial pressure can be tried hard to keep so is held in a substrate constant level.On the contrary, adjust pressure in the vacuum chamber 1 if introduce speed by pilot-gas, the oxygen partial pressure power in the vacuum chamber 1 can fluctuate so.
When the amount of oxygen in the ITO nesa coating reduced, the electric conductivity of this film reduced.In addition, the light through this film is tending towards becoming brown.Thereby the transmittance of film has also reduced.When the amount of oxygen in the ITO nesa coating increased, the light that sees through became colorless, but electric conductivity reduces.Thereby, preferably the amount of oxygen in the ITO nesa coating is adjusted to an optimum value.
For the amount of oxygen in the ITO nesa coating is adjusted to optimum value, between film stage, preferably as far as possible the oxygen partial pressure power in the vacuum chamber is maintained a constant level.Therefore, preferably the suction performance that is installed in the vacuum-pumping equipment 17 on the vacuum chamber 1 by control is adjusted the pressure in the vacuum chamber 1, because oxygen partial pressure power can be maintained a constant level.
From membrane stress with thickness increase, the angle of production cost and transmittance, the thickness of ITO nesa coating is preferably 300nm or littler, more preferably 200nm or littler.
ITO nesa coating according to the present invention can have big about 2nm of arithmetic average roughness or the littler arithmetic average roughness than the substrate before forming at the ITO nesa coating.Contrast therewith, the ITO nesa coating that obtains by sputtering method has the arithmetic average roughness than its big about 5nm.Therefore, we we can say that ITO nesa coating according to the present invention is being outstanding aspect the surface smoothness.
Therefore, polishing is implemented to make it level and smooth in unnecessary surface to the ITO nesa coating.Can the equipment (for example OLED display) that be preferred for requiring smoothness according to the substrate of ITO nesa coating of the present invention will be had.
Fig. 2 illustrates the similar ion plating device with Fig. 1, and not having substrate holder and heated substrates except the device of Fig. 2 is different positions.In the device of Fig. 2, in vacuum chamber 1, carry by the conveyer frames (not shown) by the substrate 25 of well heater 11 heating.Thereby the ITO nesa coating is formed on the substrate 25 under filming condition becomes stable status, because substrate 25 is carried above the ITO source 19 of crucible 3.
Below non-limitative example be used to explain of the present invention.
Example 1
Utilize the film deposition system of Fig. 1 on substrate, to form the ITO nesa coating, as follows.
ITO source 19 is housed in the carbon crucible 3, also, by Kojundo Chemical Lab., Co., the ITO particle (Sn:5wt% of oxide form) that Ltd. produces.The crucible 3 of charging is placed on preposition in the vacuum chamber 1.
Will be as polyethylene terephthalate (PET) film (width: 20cm of substrate 25; Thickness: 100 μ m; Trade name: polyester film E5101, by TOYOBO., LTD makes) clean and be placed on the substrate holder 4.
Then, spend about 2 hours by vacuum-pumping equipment 17 vacuum chamber 1 is bled, the pressure in vacuum chamber 1 reaches 2.0 * 10
-4Pa.Bleed operating period at this, the PET film is heated to 100 ℃ temperature.
Finish after these, the suction performance that has the vacuum-pumping equipment 17 of conductance valve 16 by control is adjusted to 0.1Pa with the pressure in the vacuum chamber 1.
After discharge, pressure and the evaporation of ITO source become stable, spent 60 seconds by the opening of flashboard and form an ITO film on the PET film.
In fact, ITO film (thickness: be that high rate of film build with 2.5nm/s forms 150nm).The heat that is radiated on the substrate is 3.3J/cm
2Min.The ITO nesa coating that obtains has the surface resistivity and 1.5 * 10 of 10 Ω/
-4The extremely low resistivity of Ω cm.
The substrate with ITO film that obtains is tested through the cross cutting adhesivity of the R of Japanese Industrial Standards (JIS) 3220.In this test, this ITO film does not peel off from substrate.Therefore, judge that this viscosity is good.
This PET film does not become curved because of forming the ITO film thereon.This ITO film does not almost have internal stress.This film is transparent, and is 83% to the transmissivity of wavelength 550nm.The arithmetic average roughness of this ITO film (Ra) is than the big 0.5nm of the substrate before forming at the ITO film.Thereby, judge that this ITO film has very level and smooth surface.
Example 2
Utilize the film deposition system of Fig. 2 on substrate, to form the ITO nesa coating, as follows.
Similar with example 1, the ITO source 19 of packing in the carbon crucible 3, also, and by Kojundo ChemicalLab., Co., the ITO particle (Sn:5wt% of oxide form) that Ltd. produces.The crucible 3 of charging is placed on preposition in the vacuum chamber 1.
Will be as polyethylene terephthalate (PET) film (width: 20cm of substrate 25; Thickness: 100 μ m; Trade name: polyester film E5101, by TOYOBO., LTD makes) clean and be placed on the conveyer frames (not shown).The PET film is heated to 100 ℃ temperature.With ITO source 19 with the same condition of example 1 under evaporate.After discharge, pressure and the evaporation of ITO source become stable, when carrying the PET film with the speed of 3.3mm/s, form the ITO film on this PET film.
In fact, the ITO film that obtains has the thickness of 150nm.The heat that is radiated on the substrate is 3.3J/cm2min.The ITO nesa coating that obtains has the surface resistivity (sheetresistance) and 1.7 * 10 of 11 Ω/
-4The extremely low resistivity of Ω cm.
The substrate with ITO film that obtains is tested through the cross cutting adhesivity of JIS R 3220.In this test, this ITO film does not peel off from substrate.Therefore, judge that this viscosity is good.
This PET film does not become curved because of forming the ITO film thereon.This ITO film does not almost have internal stress.This film is transparent, and is 83% to the transmissivity of wavelength 550nm.The arithmetic average roughness of this ITO film (Ra) is than the big 0.7nm of the substrate before forming at the ITO film.
Comparative Examples 1
On substrate, forming the ITO film, open and be used to form the ITO film for 30 seconds except the power with 7.5kW is applied to pressure gradient type plasma gun 2 and flashboard with the same mode of example 1.The ITO film that obtains has the thickness of 150nm.The heat that is radiated on the substrate is 10.2J/cm
2Min.The ITO film that obtains has crackle on whole surface.In other words, it be fracture and do not have electroconductibility.Therefore, its surface resistivity is infinitely great.
Comparative Examples 2
On substrate, forming the ITO film, except substrate 25 being heated to 50 ℃, the power of 7.5kW is applied to pressure gradient type plasma gun 2 and flashboard opens and be used to form the ITO film for 30 seconds with the same mode of example 1.
The ITO film that obtains has the thickness of 150nm.The heat that is radiated on the substrate is 10.2J/cm
2Min.The surface resistivity of different measuring position is widely different.Therefore, judge that this ITO film is inferior.
Comparative Examples 3
On substrate, to form the ITO film, except the pressure in the vacuum chamber 1 being adjusted to the 0.4Pa by the suction performance of control vacuum-pumping equipment 17 with the same mode of example 1.
The ITO film that obtains has the thickness of 145nm.The heat that is radiated on the substrate is 3.3J/cm
2Min.The ITO nesa coating of Austria have the surface resistivity and 3.5 * 10 of 24 Ω/
-4The resistivity of Ω cm.Wanting of this resistivity ratio 1 is high.
The ITO film is 82% to the transmissivity of wavelength 550nm.The arithmetic average roughness of this ITO film (Ra) is than the big 1.0nm of the substrate before forming the ITO film.
Comparative Examples 4
On substrate, to form the ITO film, except the argon gas amount of introducing vacuum chamber 1 by control is adjusted to the pressure in the vacuum chamber 1 0.1Pa with the same mode of example 1.
ITO film (thickness: be that high rate of film build with 1.5nm/s forms 150nm).Yet the ITO nesa coating that obtains has the very high surface resistance (sheet resistance) and 2.7 * 10 of 180 Ω/
-3The high resistivity of Ω cm.The only brown that sees through.
Claims (5)
1, a kind ofly on substrate, form the method for ITO nesa coating, comprise step by the ion plating device:
(a) vacuum chamber, produce beam-plasma from pressure gradient type plasma gun;
(b) with these ion beam irradiations ITO source, with heating with evaporate this ITO source;
(c) the ITO source ionization that will evaporate by plasma atmosphere; With
(d) this Ionized ITO source of deposition on this substrate, with this ITO nesa coating of formation on this substrate,
This method feature is, during step (d), the temperature of this substrate is adjusted to 80-145 ℃ at least, and at least during step (d), and the radiant heat that time per unit and per unit area incide on this substrate from this ITO source is adjusted to 1.5-10.0J/cm
2The scope of min.
2, the method for claim 1, wherein at least during step (d) in, the suction performance that is installed in the extraction equipment on this vacuum chamber by control is adjusted to 0.05-0.3Pa with the pressure in the vacuum chamber.
3, method as claimed in claim 1 or 2 wherein, in step (a) before, preheats processing to this substrate,
Wherein, during the preheating of this substrate, with the actual temperature that is connected to first this substrate of thermometer measure of this substrate temporarily,
Wherein, in the time of measuring this actual temperature, also with being arranged near this substrate and being installed in the approximate temperature of second this substrate of thermometer measure in the vacuum chamber,
Wherein produce calibration curve from this reality and approximate temperature, this calibration curve provides actual temperature by approximate temperature,
Wherein,, with this approximate temperature of second thermometer measure, and determine actual temperature, and actual temperature is adjusted to 80-145 ℃ during (d) in step (a) from this calibration curve.
4, a kind of substrate with ITO nesa coating, it is made by claim 1 or 2 described methods, and it is characterized in that, this ITO nesa coating comprises the Indium sesquioxide that is mixed with tin, the amount of tin accounts for 5-10wt%, represent with stannic oxide, and it is characterized in that this ITO nesa coating has from 1.2 * 10
-4To 3.0 * 10
-4The resistivity of Ω cm.
5, a kind of substrate with ITO nesa coating according to claim 4, it is characterized in that the arithmetic average roughness that this ITO nesa coating has is than the arithmetic average roughness big 2nm of this substrate before forming this ITO nesa coating or littler.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004340107A JP2006152322A (en) | 2004-11-25 | 2004-11-25 | Ito transparent conductive film deposition method, and substrate with ito conductive film |
| JP2004340107 | 2004-11-25 |
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| CN1800439A CN1800439A (en) | 2006-07-12 |
| CN100491583C true CN100491583C (en) | 2009-05-27 |
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| JP (1) | JP2006152322A (en) |
| KR (1) | KR100736664B1 (en) |
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| JP4686776B2 (en) * | 2006-08-28 | 2011-05-25 | Ｄｏｗａエレクトロニクス株式会社 | ITO powder and manufacturing method thereof, coating material for ITO conductive film, and transparent conductive film |
| KR101041486B1 (en) * | 2011-03-14 | 2011-06-16 | 한국기계연구원 | Method of transparent electrode and transparent electrode by the method |
| CN103543889B (en) * | 2012-07-17 | 2017-12-29 | 深圳达沃斯光电有限公司 | Monolayer capacitive touch screen preparation method |
| JP2014034699A (en) * | 2012-08-08 | 2014-02-24 | Sumitomo Heavy Ind Ltd | Film manufacturing method |
| CN104651796B (en) * | 2013-11-19 | 2017-06-06 | 北京北方微电子基地设备工艺研究中心有限责任公司 | The resistance adjustment method of ito thin film |
| JP6211557B2 (en) * | 2014-04-30 | 2017-10-11 | 日東電工株式会社 | Transparent conductive film and method for producing the same |
| KR20170005240A (en) * | 2015-07-01 | 2017-01-12 | 주식회사 아바코 | Apparatus and Method for depositing a conductive oxide layer |
| CN104962865A (en) * | 2015-07-07 | 2015-10-07 | 京浜光学制品（常熟）有限公司 | Ion-source auxiliary ITO film thermal evaporation process |
| CN105895262B (en) * | 2016-03-30 | 2018-09-21 | 武汉光谷创元电子有限公司 | Transparent conductive film and its manufacturing method |
Citations (1)
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|---|---|---|---|---|
| CN1330168A (en) * | 2000-06-21 | 2002-01-09 | 日本板硝子株式会社 | Substrate with transperant conductive film and organic electroluminescence device using the substrate |
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| JP2624778B2 (en) * | 1988-06-13 | 1997-06-25 | 株式会社トービ | High-speed production method of ITO transparent conductive film |
| JPH0925575A (en) * | 1995-07-10 | 1997-01-28 | Chugai Ro Co Ltd | Formation of ito film |
| JP3958871B2 (en) * | 1998-06-26 | 2007-08-15 | 大日本印刷株式会社 | ITO film forming method and SiOx film forming method |
| JP2000282225A (en) * | 1999-04-01 | 2000-10-10 | Nippon Sheet Glass Co Ltd | Formation of transparent electrically conductive film and transparent electrically conductive film formed by this method |
| JP2000303182A (en) * | 1999-04-16 | 2000-10-31 | Anelva Corp | Chemical vapor deposition device |
| JP2003141947A (en) * | 2001-11-06 | 2003-05-16 | Stanley Electric Co Ltd | Forming method of ito transparent electrode |
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| CN1330168A (en) * | 2000-06-21 | 2002-01-09 | 日本板硝子株式会社 | Substrate with transperant conductive film and organic electroluminescence device using the substrate |
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| KR20060058651A (en) | 2006-05-30 |
| KR100736664B1 (en) | 2007-07-06 |
| CN1800439A (en) | 2006-07-12 |
| JP2006152322A (en) | 2006-06-15 |
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