JP3074209B2 - Thin film laminated device with substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin-film laminated device, and more particularly, to a switching element which can be suitably used for a flat panel display for OA equipment and TV.

[0002]

2. Description of the Related Art There is a strong demand for use of a large-area liquid crystal panel in OA equipment terminals and liquid crystal TVs. Therefore, in the active matrix system, a switch is provided for each pixel and a device is devised so as to hold a voltage. Kaisho 61-2602
19, JP-A-62-62333). In recent years, liquid crystal panels have been actively reduced in weight and cost, and the use of plastic for the substrate of the switching element has been studied. However, when the thin film laminated switching element is formed on plastic, the plastic substrate is deformed or curled, and there is a problem such as peeling of the film. Also, when fabricating a thin-film laminated switching element, there is a photolithography step of immersing the plastic in a solution of acid, alkali, water, etc.Acid, alkali, water, etc. remain in the plastic, causing the element deterioration. became. When a thin film laminated device is formed into a fine pattern, a pattern shift occurs due to expansion and contraction of a substrate, and it has been difficult to expose a large area at a time. Further, the anisotropy of the expansion and contraction of the substrate made pattern formation more difficult. In the production of a liquid crystal display device using a plastic film substrate, it was necessary to perform an alignment method peculiar to plastic during the alignment treatment. So SiO
It is known that by forming _two layers on one side of a plastic film, orientation treatment can be performed in the same manner as a glass substrate. However, when a plastic film is coated with SiO ₂ and a thin-film laminated device is formed thereon, it is often recognized that cracks of SiO ₂ occur in a process involving heat during the production, which impairs the reliability of the thin-film laminated device. It was enough. In addition, if the thin film is formed only on one side of the plastic substrate (film), curling occurs in accordance with the internal stress of the inorganic substance thin film, causing problems such as handling. Also, JP-A-3-138617
In the publication, 20 or 20 on one side or both sides of a polymer film.
A liquid crystal display device using a substrate on which a barrier layer made of a metal oxide or metal nitride of 0A to 1000A is formed has been developed. From the above, in order to manufacture a thin film laminated device on a plastic substrate, it has become an essential technology to form a thin film made of an inorganic substance on both surfaces of the plastic substrate. However, after forming a thin film made of an inorganic material on both surfaces of a plastic substrate or after manufacturing a thin film laminated device, when the substrate is cut into a predetermined size, there is a problem that a crack is generated in the thin film made of an inorganic material. Cracking proceeds further in a later process.

[0003]

It is an object of the present invention to solve the above-mentioned conventional problems and to provide a thin and reliable thin film laminated device which is light in weight, low in cost, free of film peeling, cracks and substrate curls.

[0004]

To achieve the above object, the present inventors have:
After examining the fabrication of switching elements on lightweight and inexpensive plastics and conducting repeated research, it became clear that curling was the biggest problem in the case of plastic film deformation of the plastic substrate in the element fabrication process. Was. We also found that the causes of plastic deformation and plastic film curl were internal stress of the laminated thin film, thermal expansion and contraction of the plastic, swelling with acid, alkali, and water. It was found that it was effective to use the plastic substrate formed as described above. In addition, when the inorganic material thin film is formed on both sides of the substrate or after the thin film laminated device is manufactured and cut into a predetermined size, cracks may occur in the inorganic material thin film at the edge of the substrate. May progress. The present invention is a result of this measure. That is, the first of the present invention
Is a plastic substrate and a thin film laminated device formed on the substrate, wherein a first inorganic material layer of a thin film made of an inorganic material is provided on one surface of the substrate, and a second inorganic material layer of a thin film made of an inorganic material is provided on the other surface. The present invention relates to a thin film laminated device with a substrate, comprising: a material layer; and a polymer coating at a crack located in the first and second inorganic material layers.
A second aspect of the present invention is the method according to the first aspect, wherein at least one of the first inorganic material layer and the second inorganic material layer is a thin film made of a silicon compound containing fluorine. The present invention relates to a thin film laminated device. Third of the present invention
Are the first inorganic material layer, the plastic film substrate, the second
In the laminated structure including the inorganic material layer and the thin film laminated device, the stress of the first inorganic material layer is adjusted so as to be substantially equal to the sum of the stress of the second inorganic material layer and the stress of the thin film laminated device. A thin-film laminated device with a substrate according to claim 1 or 2. A fourth aspect of the present invention relates to the substrate-attached thin-film laminated device according to claim 1, wherein the thin-film laminated device is a MIM element using a hard carbon film as an insulating layer.

[0005] The polymer used in the present invention is preferably a thermosetting or photo-curing polymer, and particularly preferably an epoxy resin having excellent alkali resistance and acid resistance.
The inorganic material constituting the first and second inorganic material layers is SiO ₂ , SiO, Si: O: N, Si: O:
H, Si: N: H, Si: O: N: H, Si ₃ N ₄ , Ti
O ₂ , ZnS, ZnO, Al ₂ O ₃ , AlN, MgO, G
Inorganic substances such as eO, ZrO ₂ , Nb ₂ O ₅ , SiC, Ta ₂ O ₅ , or silicon compounds containing fluorine, such as SiO: F, SiO ₂ : F, SiOx: F, and Si ₃ N ₄ :
F, SiNx: F, SiON: F, SiC: F, SiO
x: sputtering of CFy or the like, vapor deposition, plasma CVD
Examples thereof include a thin film formed by a method or the like. If necessary, H ₂ may be added to the plasma during film formation.
By introducing a gas, H atoms can be bonded to Si and dangling bonds can be reduced.

[0006] SiO ₂ or SiO _{2 on} plastic substrates:
The formation of a thin film of an inorganic material such as F is important for solving problems such as peeling of a thin film laminated device formed thereon. If the thin film is formed only on one side of the plastic substrate (film), curl occurs in accordance with the internal stress of the inorganic material thin film, causing problems such as handling. In order to avoid this, it is important to form an inorganic thin film on both sides of the plastic substrate (film). Further, by forming, for example, inorganic material layers having different thicknesses on both surfaces of the plastic film substrate, the entire surface of the plastic film substrate is made concave or convex. Accordingly, it is important to make adjustments so that the upper and lower stress balances around the plastic film substrate are better maintained by the entire thin film laminated device formed thereon.

[0007] In order to manufacture the thin film laminated device of the present invention, first, S is formed on both sides of a plastic substrate (plastic film) such as polyethylene terephthalate, polyarylate, polyether sulfone, polycarbonate, polyethylene, polymethyl methacrylate, polyimide, or the like.
iO ₂ , SiO, SiON, SiO: H, SiN: H,
SiON: H, Si ₃ N ₄ , TiO ₂ , ZnS, ZnO,
Al ₂ O ₃ , AlN, MgO, GeO, ZrO ₂ , Nb ₂ O
₅ , inorganic substances such as SiC, Ta ₂ O ₅ or Si
O: F, SiO ₂ : F, SiOx: F, Si ₃ N ₄ : F,
SiNx: F, SiON: F, SiC: F, SiOx:
A fluorine-containing silicon compound such as CFy is sputtered, vapor-deposited, plasma-enhanced CVD, etc., to 300-150.
It is formed with a thickness of 00 °, preferably 1000 to 10000 ° and a predetermined stress. The formed thin film does not necessarily need to have the same inorganic substance on both sides.
The inorganic material constituting the second inorganic material layer may be selected from the group consisting of SiO ₂ and Si ₃ N ₄ , and the film thickness does not need to be the same. Particularly preferred inorganic substances are SiO ₂ , Si ₃ N ₄ , SiON, SiO: H, Si
N: H, SiON: H, AlN, SiO ₂ : F, SiO
N: F, Si ₃ N ₄ : F and the like. When the same inorganic material is used for both surfaces, that is, when the same inorganic material is used for the first inorganic material layer and the second inorganic material layer, SiO ₂ , Si ₃ N
₄ , SiON is preferred, and SiO ₂ and Si are particularly preferred.
₃ N ₄ .

In the case of forming a film with the above-mentioned fluorine-containing silicon compound, if necessary, F ₂ , HF, CF ₄ , Si
F ₄ , (CH ₃ ) ₃ SiF, (C ₆ H ₅ ) ₃ SiF, (C ₆ H ₅ ) ₂ S
If a fluorine compound such as iF ₂ is allowed to coexist, the fluorine content in the film can be controlled. Further, the fluorine content can be distributed or inclined in the film thickness direction.
Since the surface of the fluorine compound has low energy and the adhesion to the plastic or the thin film laminated device becomes small, the interface between the silicon compound containing fluorine and the plastic substrate and the thin film laminated device does not contain fluorine or contains fluorine. It is preferred to minimize the amount. As the fluorine content in the film other than the coat film interface,
In consideration of the formation of the network of the silicon compound and the rigidity of the film, 0 <F / Si <1.5 is preferable.

When the inorganic substance thin film is crystalline, moisture or the like existing in the plastic substrate may pass through the crystal grain boundaries and reach below the thin film laminated device, causing deterioration of the element. Cracks occur in the inorganic material thin film at the grain boundary in the thermal step of the fabrication process, and furthermore, when microfabricating the thin film laminated device, anisotropic expansion and contraction of the substrate based on the thermal expansion anisotropy of the inorganic material occurs In some cases, it may be difficult to form a pattern. In order to avoid these problems, it is desirable to form an amorphous thin film made of an inorganic substance on both surfaces of a plastic substrate (film). For example, in order to make an F-containing silicon compound amorphous, the substrate temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and the substrate is preferably formed by a sputtering method or a plasma CVD method. When the thin film laminated device is used for a liquid crystal display driving element, it is preferable that the transmittance of the inorganic substance is 75% or more at a wavelength of 400 to 850 nm in order to secure display contrast.

When thin films are formed on both surfaces of a plastic substrate, if the thin films are formed one by one, the substrate curls immediately after forming on only one surface. In addition, since a procedure for forming a thin film is required for each side, there is a problem in productivity and cost. Therefore, it is preferable to simultaneously form an inorganic thin film on both surfaces. Plastic thickness is 50μ
Although those having a size of m to 2 mm are used, the thickness is preferably 500 μm or less, particularly preferably 300 μm or less. Next, a thin film laminated device is formed on a plastic coated on both sides with an inorganic substance. Generally, the curl of a substrate is determined by the internal stress of a thin film formed on the substrate. Further, thermal stress generated by the temperature at the time of producing a thin film also poses a problem in a plastic film substrate having a large coefficient of linear expansion. Therefore, in order to form a thin film laminated device on a plastic substrate and obtain a flat device, a substrate configuration having a stress that cancels out the internal stress and thermal stress generated when the thin film laminated device is manufactured is required. In the case of using a substrate in which a thin film made of an inorganic substance is formed on both surfaces of the present invention, a thin film made of an inorganic substance having a stress as shown in the following formula is required. Stress of the thin film laminated device + stress of the second inorganic material layer = stress of the first inorganic material layer When the first and second inorganic substances are of the same composition and the same material, the stress is determined by the film thickness.
The adjustment of the stress of the plastic substrate having the inorganic substance formed on both sides can be easily controlled by the thickness of the inorganic substance.

As a thin film laminated device, a metal-insulator-metal MIM (Metal-Insulator) is used.
or-Metal) type element, JP-A-61-275811
MSI (Metal-Semi-
(Insulator) element, SIS (Semiconductor-Ins) having a layer structure of semiconductor-insulator-semiconductor
and MIMIM elements having a metal-insulator-metal-insulator-metal layer structure described in JP-A-64-7577.
Among them, an MIM element using a hard carbon film which can be formed at a low temperature as an insulator is advantageous. When a hard carbon film is used for the insulating layer, the plastic substrate (film) curls greatly. Therefore, it is preferable to form an inorganic material film on both surfaces of the substrate to increase the rigidity of the substrate.

Next, a method for manufacturing the device will be described in detail with reference to FIGS. First, a transparent electrode material for a pixel electrode is deposited on a plastic substrate 1 having both surfaces coated with the inorganic substance (2a, 2b) by a method such as vapor deposition or sputtering, and is patterned into a predetermined pattern.
And Next, a conductor thin film for a lower electrode is formed by a method such as vapor deposition or sputtering, and is patterned into a predetermined pattern by wet or dry etching to form a first conductor 7 serving as a lower electrode, on which a plasma CVD method and an ion beam After the hard carbon film 2 is coated by a method or the like, it is patterned into a predetermined pattern by dry etching, wet etching or a lift-off method using a resist to form an insulating film, and then a conductor for bus lines is formed thereon by a method such as vapor deposition or sputtering. A second conductor 6 which becomes a bus line is formed by coating the thin film and patterning it into a predetermined pattern,
Finally, an unnecessary portion of the lower electrode is removed to expose the transparent electrode pattern, thereby forming a pixel electrode 4. In this case, the configuration of the MIM element is not limited to this. After the MIM element is manufactured, a transparent electrode is provided on the uppermost layer, a transparent electrode also serves as an upper or lower electrode, a side surface of the lower electrode. Various modifications are possible, such as the one in which a MIM element is formed. Here, the thicknesses of the lower electrode, the upper electrode, and the transparent electrode are generally in the range of several hundreds to several thousand, several hundreds to several thousand, and several hundreds to several thousand, respectively. The thickness of the hard carbon film ranges from 100 to 8000, preferably from 200 to 6000, more preferably from 300 to 4000. In the case of a plastic substrate, it has been extremely difficult to fabricate an active matrix device using an active element because of its heat resistance. However, a hard carbon film can be produced at a substrate temperature of about room temperature, and a high quality film can be produced on a plastic substrate, which is a very effective means for improving image quality.

Next, the material of the MIM element used in the present invention will be described in more detail. As the material of the first conductor 7 serving as the lower electrode, Al, Ta, Cr, W, Mo, Pt, N
i, Ti, Cu, Au, W, ITO, ZnO: Al, In ₂ O ₃ ,
Various conductors such as SnO ₂ are used. Next, as a material of the second conductor 6 which becomes a bus line, Al, Cr, Ni, M
o, Pt, Ag, Ti, Cu, Au, W, Ta, ITO, Zn
O: Al, but In ₂ O _3, SnO ₂ and the like various conductors are used, Ni from the viewpoint of stability and reliability of the I-V characteristic is particularly excellent, Pt, Ag is preferable. It can be seen from the MIM element using the hard carbon film 2 as the insulating film that the symmetry does not change even when the type of the electrode is changed, and that the PIM has a Pool-Frenkel conduction from the relationship of 1 nI∝√v. From this fact, it can be seen that in the case of this type of MIM element, any combination of the upper electrode and the lower electrode may be used. However, depending on the adhesion between the hard carbon film and the electrode and the state of the interface, the device characteristics (I
-V characteristic). Considering these, it was found that Ni, Pt, and Ag were good.

The current-voltage characteristics of the MIM device of the present invention are shown in FIG. 4, and are approximately represented by the following conduction equations.

(Equation 1) I: Current V: Applied voltage κ: Conductivity coefficient β: Pool-Frenkel coefficient n: Carrier density μ: Carrier mobility q: Electron charge Φ: Trap depth ρ: Specific resistance d: Hard carbon film thickness (Å) k : Boltzmann constant T: ambient temperature ε ₁ : dielectric constant of hard carbon ε ₂ : vacuum dielectric constant

Next, a method for manufacturing a liquid crystal display device will be described with reference to FIG. First, on the insulating substrate 1 ', a transparent conductor for the common electrode 4', for example, ITO, ZnO: Al, ZnO: Si, Sn
Sputtering O _2, In ₂ O _3, etc., it is several μm deposited from several hundred Å by vapor deposition or the like, and patterned into a stripe shape and the common electrode 4 '. Substrate 1 'provided with this common electrode 4'
An alignment material 8 such as polyimide is attached to each surface of the substrate 1 on which the MIM elements are provided in a matrix form, a rubbing process is performed, a sealing material is attached, and a gap material 9 is inserted to make the gap constant. 3 to form a liquid crystal display device. Thus, a liquid crystal display device is obtained.

The hard carbon film used for the MIM element of the device of the present invention will be described in detail. An organic compound gas, especially a hydrocarbon gas, is used to form a hard carbon film. The phase state of these raw materials does not necessarily need to be a gaseous phase at normal temperature and normal pressure, but may be used in a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or decompression. is there. As for the hydrocarbon gas as the raw material gas, for example, CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄
Paraffinic hydrocarbons H _10, etc., acetylenic hydrocarbons such as C ₂ H _2, olefinic hydrocarbons, diolefinic hydrocarbons, even at least comprises gas using a hydrocarbon of Te to base such as an aromatic hydrocarbon It is possible. Further, other than hydrocarbons, any compounds containing at least a carbon element, such as alcohols, ketones, ethers, esters, CO, and CO ₂ can be used. As a method for forming a hard carbon film from a source gas in the present invention, a method in which a film forming active species is formed through a plasma state generated by a plasma method using a direct current, a low frequency, a high frequency, or a microwave or the like Is preferred, but for the purpose of larger area, improved uniformity, and low-temperature film formation, in order to perform deposition under low pressure,
A method utilizing the magnetic field effect is more preferable. Active species can also be formed by thermal decomposition at high temperatures. In addition, it may be formed through an ion state generated by an ionization evaporation method, an ion beam evaporation method, or the like, or may be formed from neutral particles generated by a vacuum evaporation method, a sputtering method, or the like. Alternatively, it may be formed by a combination of these.

The conditions for depositing the hard carbon film thus produced
Is as follows in the case of the plasma CVD method. RF output: 0.1-50W / cm^Two  Pressure: 10^-3Deposition temperature: room temperature to 350 ° C., preferably room temperature to 250 ° C. Due to this plasma state, the source gas is converted into radicals and ions.
Is decomposed into and reacts to form carbon atoms C on the substrate.
(Amorphous) and fine particles comprising
At least crystalline (crystal size is several tens of degrees to several μm)
A hard carbon film containing one is deposited. In addition, hard carbon film
Table 1 shows various characteristics.

[Table 1] Note) Measuring method; Specific resistance (ρ): Determined from the IV characteristics of a coplanar cell. Optical band gap (Egopt): absorption coefficient from spectral characteristics
(α) is determined and determined from the relationship of Equation 2.

(Equation 2) Hydrogen content in film [C (H)]: 29 from infrared absorption spectrum
The peak near 00 / cm is integrated and multiplied by the absorption cross section A to obtain the peak. That is, [C (H)] = A · ∫α (ν) / ν · dv SP ³ / SP ² ratio: The infrared absorption spectrum is decomposed into Gaussian functions assigned to SP ³ and SP ² respectively. Determined from the area ratio. Vickers hardness (H): According to a micro Vickers meter. Refractive index (n): Based on ellipsometer. Defect density: by ESR.

The hard carbon film thus formed was analyzed by Raman spectroscopy and IR absorption.
As shown in FIGS. 7 and 7, the carbon atom has a hybrid orbital of SP ³ and SP ²
It has been clarified that interatomic bonds that form hybrid orbitals are mixed. The ratio of SP ³ bonds to SP ² bonds can be roughly estimated by separating peaks in the IR spectrum. The IR spectrum shows 2800-3150 cm ^-1
The spectrum of many modes is overlapped and measured.
It is clear that the peaks corresponding to each wave number are assigned. As shown in FIG. 5, the peaks are separated by Gaussian distribution, the respective peak areas are calculated, and the ratio is obtained.
P ³ / SP ² can be known. According to X-ray and electron diffraction analysis, it has been found that it is in an amorphous state (aC: H) and / or an amorphous state containing fine crystal grains of about 50 ° to several μm. In general, in the case of the plasma CVD method suitable for mass production, the smaller the RF output, the higher the specific resistance and hardness of the film. The lower the pressure, the longer the lifetime of the active species. The area can be made uniform, and the specific resistance and hardness tend to increase. Furthermore, at low pressures, the plasma density decreases,
The method using the magnetic field confinement effect is particularly effective for increasing the specific resistance. Further, this method has a feature that a high-quality hard carbon film can be similarly formed even at a relatively low temperature condition of about room temperature to about 150 ° C., and is therefore most suitable for lowering the temperature of the MIM element manufacturing process. Therefore, there is a feature that a degree of freedom in selecting a substrate material to be used is widened and a uniform film can be obtained over a large area because the substrate temperature can be easily controlled. Further, as shown in Table 1, the structure and physical properties of the hard carbon film can be controlled in a wide range, and therefore, there is an advantage that device characteristics can be freely designed. Further, the relative dielectric constant of the film is 2 to 6, which is Ta ₂ used for the conventional MIM element.
Since it is smaller than O ₅ , Al ₂ O ₃ , and SiNx, when manufacturing an element having the same electric capacity, the element size can be large, so that fine processing is not so required and the yield is improved (driving conditions) Therefore, the capacitance ratio between the LCD and the MIM element needs to be about C (LCD) / C (MIM) = 10: 1).

The steepness of the element is expressed as β∝1 / √ε · √d
Therefore, if the relative permittivity ε is small, the steepness increases, and the ratio between the on-current Ion and the off-current Ioff can be increased. LCD with lower duty ratio
Driving becomes possible, and a high-density LCD can be realized. Further, since the hardness of the film is high, the damage due to the rubbing step at the time of enclosing the liquid crystal material is small, and the yield is also improved from this point. In view of the above points, the use of a hard carbon film makes it possible to realize a low-cost, gradation (color) and high-density LCD.

Further, in addition to carbon atoms and hydrogen atoms, the hard carbon film is composed of a group III element, a group IV element, a group V element, an alkali metal element, an alkaline earth metal element and a nitrogen atom of the periodic table. , An oxygen element, a chalcogen element, or a halogen atom as a constituent element. As one of the constituent elements, those in which Group III element of the periodic table, Group V element, alkali metal element, alkaline earth metal element, nitrogen atom or oxygen atom are introduced are those in which the thickness of the hard carbon film is non-doped The thickness can be increased by about 2 to 3 times as compared with the above, and thereby, the generation of pinholes at the time of manufacturing the device can be prevented, and the mechanical strength of the device can be remarkably improved. Further, in the case of a nitrogen atom or an oxygen atom, the same effect as in the case of a group IV element of the periodic table as described below is obtained.
In the same way, the elements incorporating a Group IV element of the periodic table, a chalcogen-based element or a halogen element significantly improve the stability of the hard carbon film and also improve the hardness of the film. Can be produced. These effects are obtained because the group IV element and the chalcogen element reduce the active double bond existing in the hard carbon film, and in the case of the halogen element, 1) abstraction with respect to hydrogen. The reaction promotes the decomposition of the source gas to reduce dangling bonds in the film, and 2) the halogen element X
The hydrogen in the -H bond is extracted and replaced by the hydrogen, enters the film as a C-X bond, and the binding energy increases (C-H
This is because the bonding energy between C and X is larger between C and X).

In order to make these elements the constituent elements of the film, in addition to hydrocarbon gas and hydrogen as the raw material gas, a group III element, a group IV element and a group IV element in the periodic table as a dopant are contained in the film as a dopant. In order to contain a Group V element, an alkali metal element, an alkaline earth metal element, a nitrogen atom, an oxygen atom, a chalcogen element or a halogen element, a compound (or molecule) containing these elements or atoms (hereinafter referred to as "Other compounds" may be used. Here, as the compound containing a Group III element of the periodic table, for example, B (O
_{C 2 H 5) 3, B} 2 H 6, BCl 3, BBr 3, BF 3, Al (O-i-
C ₃ H ₇ ) ₃ , (CH ₃ ) ₃ Al, (C ₂ H ₅ ) ₃ Al, (i-C ₄ H ₉ ) ₃ A
_{l, AlCl 3, Ga (O} -i-C 3 H 7) 3, (CH 3) 3 Ga, (C
_{2 H 5) 3 Ga, GaCl} 3, GaBr 3, (O-i-C 3 H 7) 3 In,
(C ₂ H ₅ ) ₃ In and the like. Examples of the compound containing a Group IV element of the periodic table include Si ₂ H ₆ , (C ₂ H ₅ ) ₃ SiH, and Si.
F ₄ , SiH ₂ Cl ₂ , SiCl ₄ , Si (OCH ₃ ) ₄ , Si (OC _{2
H 5) 4, Si (OC} 3 H 7) 4, GeCl 4, GeH 4, Ge (OC 2
_{H 5) 4, Ge (C} 2 H 5) 4, (CH 3) 4 Sn, (C 2 H 5) 4 Sn, Sn
Cl _{4 and the} like. Examples of compounds containing Group V elements of the periodic table include PH ₃ , PF ₃ , PF ₅ , PCl ₂ F ₃ , PCl ₃ , P
Cl ₂ F, PBr ₃ , PO (OCH ₃ ) ₃ , P (C ₂ H ₅ ) ₃ , PO
Cl ₃ , AsH ₃ , AsCl ₃ , AsBr ₃ , AsF ₃ , AsF ₅ , A
sCl ₃ , SbH ₃ , SbF ₃ , SbCl ₃ , Sb (OC ₂ H ₅ ) _{3 and the} like. As the compound containing an alkali metal atom, there is for example _{LiO-i-C 3 H 7} , NaO-i-C 3 H 7, KO-i-C 3 H 7 or the like. Examples of the compound containing an alkaline earth metal atom include Ca (OC ₂ H ₅ ) ₃ , Mg (OC ₂ H ₅ ) ₂ , and (C ₂ H ₅ ) ₂ Mg. Examples of the compound containing a nitrogen atom include nitrogen gas, inorganic compounds such as ammonia, organic compounds having a functional group such as an amino group and a cyano group, and heterocycles containing nitrogen. Examples of the compound containing an oxygen atom include oxygen gas, ozone, water (steam), hydrogen peroxide, carbon monoxide,
Inorganic compounds such as carbon dioxide, carbon monoxide, nitric oxide, nitrogen dioxide, nitrous oxide, nitrous oxide, nitric oxide, etc., hydroxyl group, aldehyde group, acyl group, ketone group, nitro group, nitroso group, sulfone An organic compound having a functional group or a bond such as a group, an ether bond, an ester bond, a peptide bond, a heterocyclic ring containing oxygen, and a metal alkoxide may be used. Examples of the compound containing a chalcogen-based element include H ₂ S, (CH ₃ ) (CH ₂ ) ₄ S (CH ₂ ) ₄ CH ₃ ,
CH ₂ ＣＨCHCH ₂ SCH ₂ CH ＝ CH ₂ , C ₂ H ₅ SC
_{2 H 5, C 2 H 5} SCH 3, _{thiophene, H 2 Se, (C 2} H 5) 2
Se, H ₂ Te and the like. Compounds containing a halogen element include, for example, fluorine, chlorine, bromine, iodine, hydrogen fluoride,
Carbon fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, hydrogen chloride,
Inorganic compounds such as bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, and hydrogen iodide, and organic compounds such as alkyl halide, aryl halide, styrene halide, polymethylene halide, and haloform are used. Liquid crystal drive MIM
A hard carbon film suitable for an element has a thickness of 10
Advantageously, the resistivity is in the range of 0 to 8000 ° and a specific resistance of 10 ⁶ to 10 ¹³ Ω · cm. In addition, drive voltage and withstand voltage (dielectric breakdown voltage)
In consideration of the margin with respect to the thickness, it is desirable that the film thickness is 200 mm or more. In order to prevent color unevenness caused by a step (cell gap difference) between the pixel portion and the thin-film two-terminal element portion from becoming a practical problem. Since the film thickness is desirably 6000 ° or less, it is more preferable that the thickness of the hard carbon film is 200 to 6000 ° and the specific resistance is 5 × 10 ⁶ to 10 ¹³ Ω · cm. The number of element defects due to pinholes in the hard carbon film increases with decreasing film thickness, and becomes particularly significant below 300 mm (defect rate exceeds 1%), and the uniformity of the in-plane distribution of film thickness. (Thus, the accuracy of film thickness control is limited to about 30 mm, and the variation in film thickness exceeds 10%), so it is more preferable that the film thickness is 300 mm or more. . Further, in order to make it difficult for the hard carbon film to peel off due to stress and to drive at a lower duty ratio (preferably 1/1000 or less), the film thickness is more preferably 4000 ° or less. In consideration of these factors, it is more preferable that the hard carbon film has a thickness of 300 to 4000 ° and a specific resistivity of 10 ⁷ to 10 ¹¹ Ω · cm.

[0022]

EXAMPLES Examples of the present invention will be described, but the present invention is not limited to these examples. Polyether sulfone 1 of 100μm thickness, as shown in Example 1 1, using a double-sided simultaneous sputtering apparatus as shown in FIG. 8, both sides at the same time Si ₃ N ₄ of approximately 5000Å thick by sputtering Si ₃ An N ₄ layer (2a, 2b) was formed. When this substrate was cut into a predetermined size, cracks occurred in the Si ₃ N ₄ at the end. To prevent this crack from progressing, the cracked part was covered with epoxy resin and
Cured at 0 ° C. for 30 minutes {FIG. 1- (b)}. Next, Si
₃ N ₄ about 1000Å by sputtering ITO on
After the thick deposition, patterning was performed to form a pixel electrode. Next, a MIM element was provided as follows. First, Al is deposited to a thickness of about 1000 mm by vapor deposition and patterned to form a lower electrode 7. A hard carbon film is deposited thereon as an insulating layer 2 to a thickness of about 1000 mm by a plasma CVD method. Patterned by etching. The conditions for forming the hard carbon film at this time are as follows. Pressure: 0.035 Torr CH ₄ Flow rate: 10 SCCM RF power: 0.2 W / cm ² Further, Ni was deposited thereon by an EB evaporation method to a thickness of about 1000 ° and then patterned to form an upper electrode 6. In the MIM device manufactured as described above, the crack of Si ₃ N _{4 at} the edge of the substrate did not progress in the subsequent process, so that the reliability of the device was improved. Embodiment 2 As shown in FIG. 3, a transparent conductor ITO for a common electrode 4 'is deposited on an insulating substrate 1' by 650 DEG using a sputtering apparatus and patterned in a stripe shape to form a common electrode 4 '.
And A rubbing treatment is performed by attaching an orientation material 8 such as polyimide to each surface of the insulating substrate 1 'provided with the common electrode 4' and the base provided with the MIM elements manufactured in Example 1 in a matrix form. Then, a gap material 9 was put in the gap to make the gap constant, and the liquid crystal 3 was sealed to produce a liquid crystal display device. This liquid crystal display device is lightweight and highly flexible, so that a high-definition display can be produced even on a curved surface which has been conventionally difficult to use.

[0023]

The present invention is configured as described above. Therefore, the thin-film laminated device with a substrate according to the present invention has no deformation, curl, etc. of the substrate, can achieve low cost and light weight, and can achieve thin-film lamination. When the device is a MIM type device using a hard carbon film as an insulating layer, the hard carbon film is manufactured by a gas phase synthesis method such as a plasma CVD method. Therefore, the degree of freedom in device design is large.2) Hard and thick film can be formed, so it is hard to be damaged mechanically, and reduction of pinholes due to thick film can be expected. 3) Good quality even at low temperature around room temperature. There is no restriction on the material of the substrate because it can form a thin film. 4) It is suitable for thin film devices because of its excellent uniformity of film thickness and film quality. 5) It has a low dielectric constant, so it has advanced microfabrication technology. Does not require This is advantageous for increasing the area of the device, and because of its low dielectric constant, the steepness of the device is high and the Ion / Ioff ratio can be taken, so that it can be driven at a low duty ratio. Particularly, it is suitable as a highly reliable switching element for a liquid crystal display, and is extremely useful in industry.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing the structure of a thin film device with a substrate according to the present invention. FIG. 1 (a) is a model diagram showing cracks generated when cutting a substrate, and FIG. Case).

FIG. 2 is an explanatory view of a main part of an MIM element constituted by a thin film device with a substrate according to the present invention.

FIG. 3 is a partial cross-sectional perspective view of a liquid crystal display device incorporating the thin film device with a substrate according to the present invention.

FIGS. 4A and 4B are graphs respectively showing an IV characteristic curve and an lnI-√v characteristic curve of the MIM element.

FIG. 5 shows a Gaussian distribution of an IR spectrum of a hard carbon film used for an insulating layer of the MIM element of the present invention.

FIG. 6 is a spectrum diagram showing an analysis result obtained by analyzing a hard carbon film used as an insulating layer of the MIM element of the present invention by a Raman spectrum method.

FIG. 7 is a spectrum diagram showing an analysis result obtained by analyzing a hard carbon film used as an insulating layer of the MIM element of the present invention by an IR absorption method.

FIG. 8 is an explanatory diagram of a double-sided simultaneous sputtering apparatus used in the manufacturing method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 plastic substrate 1 ′ plastic substrate 2 hard carbon film 2 a inorganic material layer 2 b inorganic material layer 3 liquid crystal 4 pixel electrode 4 ′ common electrode 5 active element (MIM element) 6 second conductor (bus line) (upper electrode) 7 first Conductor (lower electrode) 8 Alignment film 9 Gap material 10 Sputter target 11 Substrate holder 12 Vacuum chamber

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuji Kimura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Kenji Kameyama 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (56) References Jpn. Sho 62-63720 (JP, U) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02F 1/1333 500

Claims (4)

(57) [Claims] 1. A plastic substrate and a thin film laminated device formed on the substrate, wherein a first inorganic material layer of a thin film made of an inorganic material is provided on one surface of the substrate, and a thin film made of an inorganic material is provided on the other surface. A thin-film laminated device with a substrate, comprising: a second inorganic material layer; and a polymer coating at a crack located in the first and second inorganic material layers. 2. The thin film laminated device with a substrate according to claim 1, wherein at least one of the first inorganic material layer and the second inorganic material layer is a thin film made of a silicon compound containing fluorine. . 3. A laminated structure comprising a first inorganic material layer, a plastic film substrate, a second inorganic material layer and a thin film laminated device, wherein the stress of the first inorganic material layer is equal to the stress of the second inorganic material layer and the thin film laminated device. 3. The thin-film laminated device with a substrate according to claim 1, wherein the device is adjusted so as to be substantially equal to a total value of the stress of the substrate. 4. The thin-film laminated device with a substrate according to claim 1, wherein the thin-film laminated device is a MIM element using a hard carbon film as an insulating layer.