JP2000313970A - Formation of ceramic thin film layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a thin film layer capable of safely and continuously working a substrate by a simple process, and by which a thin ceramic layer of <=10 μm is formed. SOLUTION: The hyperfine powder with <=100 nm particle size of ceramic, e.g. of metallic oxide, metallic nitride, metallic carbide, metallic boride, metallic sulfide or the like is jetted as a mixed fluid with compressed gas of >=20 m/sec wind velocity, by which a ceramic thin film layer of <=10 μm film thickness is formed on the surface of metal, ceramic, glass, a silicon wafer, crystal, a compd. semiconductor, plastic or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating layer, a dielectric layer, a semiconductor layer, a transparent conductive layer, which has been used for manufacturing semiconductors, displays, solar cells and the like and for hardening surfaces of metals and the like.
Regarding the formation of a ceramic thin film layer used for the wear-resistant coating layer, more specifically, a metal oxide, a metal nitride, a metal carbide, a metal boride, a metal sulfide, etc., having a particle diameter of 100 nm or less. The present invention relates to a method for forming a ceramic thin film layer having a thickness of 10 μm or less on a surface of metal, ceramic, glass, silicon wafer, crystal, compound semiconductor, plastic, or the like by injecting fine powder as a mixed fluid with a compressed gas. is there.

[0002]

2. Description of the Related Art Conventionally, as a method of forming a thin film layer such as an insulating layer, a dielectric layer, a semiconductor layer, a transparent conductive layer, and a wear-resistant coating layer, a physical vapor deposition method generally called PVD,
There is a chemical vapor deposition method called D. The PVD method includes vacuum deposition, molecular beam evitaxy, ion plating,
There is sputter deposition. In vacuum deposition, a deposition source is thermally evaporated and sublimated in a vacuum to form deposition particles, the deposition particles are transported to a substrate, and the deposition particles are deposited and deposited on the substrate to form a thin film. In molecular beam epitaxy (epitaxial), a film is formed in an ultra-high vacuum by allowing a molecular beam of a raw material emitted from a molecular beam source from a Knudsen cell or the like to reach the substrate surface. Ion plating ionizes and accelerates a part of the generated vapor-deposited particles, and irradiates the substrate placed in a vacuum with the vapor-deposited particles and their ions to form a thin film on the substrate. In sputter deposition, when a target is irradiated with high-energy particles, target constituent atoms emitted from the target are transported onto a substrate to form a thin film.

[0003] CVD methods include thermal CVD and plasma CVD.
There is. In thermal CVD, a raw material gas is thermally decomposed on a substrate surface or a gas phase heated to an appropriate temperature by thermal energy with respect to a thin film constituting material supplied by a gas, and a thin film is formed by a decomposition product or a chemical reaction. . In plasma CVD, when a raw material gas at a certain pressure is discharged into a plasma state, chemically active ions and radicals are generated, and the active particles promote a chemical reaction on the substrate surface to form a thin film.

[0004]

In the PVD method such as vacuum deposition, molecular beam arbitration, ion plating, sputter deposition, etc., since operations are performed in a high vacuum, work such as heating is performed in a high vacuum resistant device. The apparatus becomes expensive, and it is difficult to continuously transport a substrate as a workpiece to the vacuum processing apparatus for processing. Further, when processing a large-sized substrate, it takes a long time to completely evacuate the inside of the apparatus, and there is a disadvantage that productivity is reduced.

In the CVD method, since a thin film is formed using a gas, it is necessary to completely shut off the outside from the outside. Therefore PVD
It becomes difficult to continuously transport the substrate into the processing apparatus in the same manner as described above. In addition, the gas used is toxic or very ignitable,
Gas management becomes complicated.

[0006] Therefore, there has been a demand for the development of a method of forming a thin film layer that can safely and continuously process a substrate by a relatively simple process.

[0007]

SUMMARY OF THE INVENTION As a method for forming a thin ceramic layer of 10 μm or less without using a vacuum apparatus, the present invention relates to metal oxides, metal nitrides, metal carbides, and the like.
The particle size of ceramics such as metal borides and metal sulfides is 100
By injecting ultrafine powder of nm or less as a mixed fluid with compressed gas whose wind speed is 20 m / sec or more, metal, ceramic, glass, silicon wafer, crystal, compound semiconductor,
The present invention relates to a method for forming a ceramic thin film layer having a thickness of 10 μm or less on a surface of plastic or the like.

In general, the adhesive force between particles and the adhesive force between particles and a substrate include a liquid crosslinking force, a van der Waals force, and an electrostatic force.
The smaller the particle size, the larger the surface area and accordingly the surface energy. Also, generally ultrafine particles of 100 nm or less, fusion of ultrafine particles,
It starts at a lower temperature when compared to the larger particle size. Particles are jetted with a compressed gas and collide with the substrate to generate a compressive stress and a shear stress, and generate heat at the same time.

Adhesion occurs due to the impact force and heat generation. The smaller the particle size, the larger the surface energy.
Since the fusion is performed at a low temperature, the adhesion to the substrate is high, and the adhesion due to the impact between the particles is also high.

When an actual test was conducted,
It has been found that the bonding strength due to the adhesion between the ceramic base material and the ceramic particles, preferably having a particle size of 50 nm or less, is extremely high.

As a device to be used, a large-scale device such as a vacuum device is not required only with an injection device, and gas management is not required since the device is processed with powder. Further, a ceramic layer having a size of 10 μm or less can be easily formed on the surface of a large workpiece by continuous conveyance and continuous processing as a processing step.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As a device for forming a thin film layer using ceramic fine powder, a known sandblasting device is used, and as shown in step 1 of FIG. Is sprayed onto the workpiece 1 as a mixed fluid, and adheres to the base material by the impact force when the workpiece 1 collides with the workpiece 1. Further, the particles adhere to each other to form a ceramic layer 8 having a film thickness of 10 μm or less.

As a sand blasting device, a known suction type in which a ceramic ultra-fine powder is drawn into a nozzle by utilizing an ejector phenomenon inside the nozzle and jetted, or a direct pressure type blasting device in which a pressure is applied to the ultra-fine powder to jet the same. Can be used.

A test was conducted on the adhesion of the ceramic powder depending on the particle size under the following conditions.

Apparatus used: SC-4S type manufactured by Fuji Seisakusho Nozzle used: suction type φ7 mm nozzle Processing pressure: 4 kg / cm ² Nozzle distance: 80 mm Glass substrate size: 150 mm × 150 mm Thickness: 3 mm Ceramic tested: TiO ₂ , ZnO, BaTiO ₃ , SiO ₂ , TiO
₂ , Al ₂ O ₃ , Fe ₂ O ₃ , ZrO _{2 An} average particle size of 20 to 100 nm, 110 to 150 nm, 1 μm ceramic is subjected to an injection test, and a 1 mm width line from the thin film layer to the base material is cut by a cutter. When 11 pieces were crossed and pulled, a 15 mm cellophane tape was stuck from the top of the thin film layer, and an adhesion strength test was performed to peel off at a stretch. I understand.

As a method for forming ceramic particles, there are a fragmentation method and a growth method. The fragmentation method is a method of obtaining fine particles by grinding, but it is difficult to obtain fine particles efficiently when the particle size is 1 μm or less. Become. In the growth method, particles are formed from ions, atoms, and molecules by two processes of nucleation and growth, and ultrafine particles having a particle size of 1 μm or less can be easily obtained. Therefore, a growth method is used as a method for obtaining ultrafine particles. The growth method is further classified into a liquid phase method and a gas phase method.

In the gas phase method, various forms of solids are deposited by condensation of component vapors and chemical reaction of gas components.

Si as an ultrafine powder of ceramic to be prepared
₃ N ₄ , TiN, ZrN, VN, AlN, BN, NbN, TaN, Zr ₃ N ₄ , SiC, T
iC, TaC, NbC, Mo ₂ C, WC, ZrC, SiO ₂ , TiO ₂ , Al ₂ O ₃ , Fe
₂ O ₃ , ZrO ₂ , NiO, CoO, SnO ₂ , Nb ₂ O ₅ , MoO ₃ , WO ₃ , B ₂ O ₃ , V
₂ O ₅ , ZnO, Cr ₂ O ₃ , NiFe ₂ O ₄ , HfO ₂ , HfO ₂ , ThO ₂ , Y ₂ O ₃ , D
_{y 2 O 3, Yb 2 O} 3, MgO, there are ITO.

The liquid phase method is a method of forming fine particles from a metal salt solution, and is roughly classified into a precipitation method and a solvent evaporation method.

In the liquid phase method, the composition can be easily controlled, and the synthesis of multi-component compound particles and the addition of trace components are easier than in the gas phase method. BaTiO ₃ , Sr as super fine powder of ceramic to be created
TiO ₃ , BaZrO ₃ , Ba (Ti _1-x Zr _x ) O ₃ , Sr (Ti _1-x Zr _x ) O ₃ , (Ba
_1-x Sr _x ) TiO ₃ , MnFe ₂ O ₄ , CoFe ₂ O ₄ , NiFe ₂ O ₄ , ZnFe ₂ O ₄ , (M
n _1-x Zn _x ) Fe ₂ O ₄ , Zn ₂ GeO ₄ , PbWO ₄ , SrAs ₂ O ₆ , BaSnO ₃ , SrS
nO ₃ , PbSnO ₃ , CaSnO ₃ , MgSnO ₃ , SrGeO ₃ , PbGeO ₃ , SrTeO
₃ , Pb (Ti _1-x Zr _x ) O ₃ , Pb _1-x La _x (Zr _y Ti _1-y ) _{1-x / 4} O ₃ , Sr (Zn
_1/3 Nb _2/3 ) O ₃ , Ba (Zn _1/3 Nb _2/3 ) O ₃ , Sr (Zn _1/3 Ta _2/3 ) O ₃ , Ba
(Zn _1/3 Ta _2/3 ) O ₃ , Sr (Fe _1/2 Sb _1/2 ) O ₃ , Ba (Fe _1/2 Sb _1/2 ) O ₃ ,
Sr (Co _1/3 Sb _2/3 ) O ₃ , Ba (Co _1/3 Sb _2/3 ) O ₃ , Sr (Ni _1/3 S
b _2/3 ) O ₃ , NiFe ₂ O ₄ , CuFe ₂ O ₄ , MgFe ₂ O ₄ (Ni _1-x Zn _x ) Fe ₂ O ₄ ,
(Co _1-x Zn _x ) Fe ₂ O ₄ , BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ , PbFe ₁₂ O ₁₉ , R
₃ Fe ₅ O ₁₂ (R = Sm, Gd, Y, Eu, Tb), Tb ₃ Al ₅ O ₁₂ , R ₃ Gd ₅ O ₁₂ (R
= Sm, Gd, Y, Er), RFeO ₃ (R = Sm, Y, La, Nb, Gd, Tb), L
aAlO ₃ , NbAlO ₃ , R ₄ Al ₂ O ₉ (R = Sm, Eu, Gd, Tb), Co ₃ As
₂ O ₈ , (Ba _x Sr _1-x ) Nb ₂ O ₆ , PZT, GeO ₂ , PbO, As ₂ O ₃ , Sb ₂ O ₅ ,
Bi ₂ O ₃ , TeO ₂ , CuO, ZnO, TiO ₂ , ZrO ₂ , Mn ₃ O ₄ , Fe ₃ O ₄ , C
oAl ₂ O ₄ , Cu ₂ Cr ₂ O ₄ , PbCrO ₄ , PbCrO ₄ , CoFe ₂ O ₄ , MgFe
₂ O ₄ , (Mg, Mn) Fe ₂ O ₄ , MnFe ₂ O ₄ , (Mn, Zn) Fe ₂ O ₄ , (Ni, Zn) Fe
₂ O ₄ , ZnFe ₂ O ₄ and the like.

A metal oxide having a particle size of 100 nm or less, preferably 50 nm or less, produced by these gas phase method and liquid phase method;
Metal nitrides, metal carbides, metal borides, metal sulfides and other ceramics have a particle size of 100 nm or less by injecting ultrafine powder with a compressed gas to produce metals, ceramics, glass,
By attaching ceramic to the surface of silicon wafer, crystal, compound semiconductor, plastic, etc., the film thickness becomes 1
A ceramic thin film layer of 0 μm or less is formed.

Example 1 Formation of Zinc Oxide Thin Film Layer As shown in FIG. 1, zinc oxide powder (ceramic ultrafine powder 15) having an average particle size of 20 nm was applied to a silicon wafer (workpiece 1) under high-pressure compressed air under the following conditions. To form a zinc oxide layer having a thickness of 1 μm.

Adhesion processing conditions Apparatus used: SCM-1ADE-401 manufactured by Fuji Manufacturing Co., Ltd. Injection pressure: 5 kg / cm ² Nozzle distance: 80 mm Nozzle tip diameter: 7 mm Example 2 Reflection for increasing brightness on the back plate of plasma display A titanium oxide layer is formed around the partition wall for the purpose of forming a layer and forming a protective layer of the address electrode.

After patterning the glass substrate with a photosensitive dry film for sandblasting and forming masking, the glass substrate is processed by sandblasting to form a plasma display partition having a depth of 120 μm, a pitch of 220 μm, and a partition width of 50 μm. Was formed.

That is, as shown in FIGS. 3 and 4, a groove having a width of 170 .mu.m and a depth of 120 .mu.m is formed at a pitch of 220 .mu.m in a center of 150 mm.times.250 mm in a center on a 200 mm.times.300 mm and 3 mm thick soda glass. Processing to form a grooved glass sheet.

After laminating the dry film 6 on the processed glass substrate by the dry film laminator 10 in step 2, it is heated to 100 ° C. in step 3 to soften the dry film and bring the dry film into close contact with the groove. Was.

Next, in step 4, a parallel light beam is applied to the center of the groove at 80 μm.
A glass mask 18 having a pattern such that only the m was not exposed to the ultraviolet light was placed thereon, and the ultraviolet exposure was performed.

In step 5, 0.3% aqueous solution of sodium carbonate 1
The development was performed in step 6, and the dry film was patterned without the dry film only in the center of the groove.

A suction pressure of 5 kg / cm ² and a pressure of 2 kg / cm ²
Injection of tin beads (low-melting metal powder) with an average particle size of 15 μm using a Fuji Hyper nozzle at cm ²
A 0 μm, about 1 μm thick tin film is formed in the trench.

In steps 8 to 10, after the dry film was peeled off with a stripping solution 19, electroplating was performed on tin (low melting point metal) patterned in step 10 to form a 6 μm thick nickel (patterned). Heat resistant metal 5)
On tin. As a result, address electrodes were formed on the rear substrate of the plasma display in which glass was directly processed.

As shown in FIG. 2, the glass substrate 2 serving as the back plate of the plasma display on which the address electrodes have been formed in the above-described steps is subjected to a
The resist 3 was solid-printed thereon by screen printing to form a resist layer 4 only on the upper part of the partition. Powder (average particle size 7 nm) titanium oxide layer of injected thickness 3μm the titanium oxide from the suction-type nozzle 21 (Ti0 ₂₎ (metal compound layer 8) was formed on the inner side of the partition wall in the steps 3 and 4.

In step 5, the resist layer was removed.

Titanium oxide was used as a white pigment, became a reflective layer when discharging, and could be used as a protective layer of the electrode.

Apparatus used: SCM-5ADNH-401 manufactured by Fuji Manufacturing Co., Ltd. Injection pressure: 5 kg / cm ² Nozzle distance: 80 mm Nozzle tip diameter: 7 mm

[Brief description of the drawings]

FIG. 1 illustrates a ceramic thin film formed thereon.

FIG. 2 is a process diagram of jetting ultrafine titanium oxide powder for the purpose of light reflection and a protective layer after forming a partition of a plasma display by processing a glass plate.

FIG. 3 is a view showing a process of forming a back plate of a plasma display by directly sandblasting a glass plate, forming a low-melting-point metal pattern in the processed groove, and performing electroplating to form an electrode; Show.

FIG. 4 shows steps 8 to 10 of the above steps.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 workpiece 2 back plate with electrodes of plasma display electrode formed directly by processing a glass plate to form a partition 3 resist 4 patterned resist 8 ceramic thin film layer 15 mixed fluid of ceramic fine powder and compressed gas

Claims (1)

[Claims] 1. A ceramic having a particle size of 100 nm, such as a metal oxide, a metal nitride, a metal carbide, a metal boride, or a metal sulfide.
By injecting the following ultrafine powder as a mixed fluid with a compressed gas having a wind speed of 20 m / sec or more, metal, ceramic, glass, silicon wafer, crystal, compound semiconductor,
The thickness of the ceramic is 10μ on the surface of plastic etc.
A method for forming a ceramic thin film layer, wherein the ceramic thin film layer is adhered to a thickness of not more than m.