JP3209633B2 - Thin film capacitor and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a miniaturized thin film capacitor having a perovskite crystal layer and a method of manufacturing the same.

[0002]

2. Description of the Related Art Barium titanate (BaTiO ₃ ) -based ceramics having a perovskite-type crystal structure are widely used mainly for capacitor materials because of their high resistivity and excellent dielectric properties. On the other hand, strontium titanate (SrTiO ₃ ) is cubic at a temperature of about 110 K or higher and is a paraelectric substance. Ceramics based on strontium titanate have a lower dielectric constant than barium titanate-based ceramics, but have the characteristics of good temperature characteristics and low dielectric loss. In addition, by shifting the Curie point by adding an additive such as barium or lead, a ceramic having a paraelectric property and a high dielectric constant at room temperature can be obtained, and is widely used as a capacitor for high frequency and high voltage. Further, is one of the typical relaxor ferroelectric _{Pb (Mg 1/3, Nb 2/3)} O 3 and a composite material of lead titanate _{Pb {(Mg 1/3,} Nb 2/3 ) _1-y
Since the composite perovskite structure compound of Ti _y ｝ O ₃ has a large relative dielectric constant and good DC bias characteristics as compared with a barium titanate-based dielectric, it has been applied to small-sized large-capacity multilayer capacitors and the like.

In recent years, with the trend toward smaller and lighter electronic components and higher integration of semiconductor devices, barium titanate-based dielectric materials, strontium titanate-based dielectric materials,
Compact and large-capacity capacitor by thinning oxide material of perovskite type crystal structure with large dielectric constant such as Pb ｛(Mg _1/3 , Nb _2/3 ) _1-y Ti _y ｝ O ₃ dielectric material Since it is possible to produce a thin film, research on thinning by various methods has been actively conducted.

As a method of forming the dielectric thin film, a sputtering method has been conventionally used (for example, K. Iijima e
tal., J. Appl. phys., vol. 60, No. 1, pp 361-367 (1986)).
However, there are problems such as a low deposition rate (<10 nm / min), an expensive single crystal substrate such as MgO is required, and composition control is difficult. Sol, which has been actively researched recently
The gel method is easy to control the composition and is suitable as a method for forming a multi-component thin film, but has problems in film quality and step coverage, and is not suitable as an industrial production technique. The CVD method has advantages such as easy composition control, film formation on a large-area substrate, and good step coverage, and is an excellent method for forming a perovskite-type dielectric thin film (for example, M. Okada et al., Jpn.J. Appl.phys., Vol.
28, No. 6, pp 1030-1034 (1989)). In addition, high-speed film formation can be performed by nearly one digit compared to the sputtering method. However, CVD
The film forming rate of the dielectric thin film by the method is about 3 μm / h, for example, a dielectric layer having a thickness of 2 μm [for example, BaT
It takes about 40 minutes to form [iO ₃ ] (for example, BS
Kwak et al., J. Appl.phys., Vol. 69, No. 2, pp 767-772 (199
1)). Therefore, in order to produce an inexpensive thin film capacitor, it is necessary to form the film at a higher speed. Also, in any of the film forming methods such as the sputtering method and the CVD method, when a dielectric thin film is formed directly on a metal substrate or a metal thin film as an electrode, a layer having poor crystallinity (initial layer) is formed at an early stage of film growth. Exists. When the capacitance is increased by making the dielectric layer of the capacitor thinner, that is, thinner, the electric characteristics are deteriorated due to the presence of the initial layer.

[0005] On the other hand, the plasma CVD method is a film forming method utilizing the activity of plasma and the CVD reaction.
Compared to the VD method, it enables low-temperature deposition and high-speed deposition (for example, E. Fujii et al., Jpn. J. Appl. Phys., Vol. 3
2, No. 10B, pp1527-1529 (1993), and A. Tomozawa et.
al., Journal of Magnetic Society of Japan, vol.17, N
o.2, pp319-322 (1993)).

[0006]

However, in the conventional plasma CVD method, even when the above-mentioned dielectric thin film is formed, the crystallinity is not excellent in the initial stage of film growth, as in the case of the sputtering method or the CVD method. There is an initial layer. For this reason, the oxide thin film having the perovskite crystal structure is (10
It is necessary to grow epitaxially on a single crystal substrate such as NaCl cut out on the (0) plane or LaAlO ₃ cut out on the (001) plane, which is expensive.

In order to solve the above-mentioned conventional problems, the present invention provides a low-cost thin-film capacitor exhibiting high crystallinity and orientation from the beginning of film formation, and a thin-film capacitor capable of miniaturization and large capacity. It is an object of the present invention to provide a manufacturing method thereof.

[0008]

In order to achieve the above object, a thin film capacitor according to the present invention has a lower electrode formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, and directly or indirectly forms a lower electrode thereon. A thin film capacitor in which a dielectric thin film layer is formed indirectly and an upper electrode is directly or indirectly formed thereon, wherein the dielectric thin film layer has
A perovskite-type dielectric thin film layer oriented on a (100) plane, and a metal substrate or a non-electrode substrate as the electrode;
Between the plate and the lower electrode or between the lower electrode and the dielectric thin film layer.
Somewhere in between , the (100) oriented NaC
It is characterized by having at least one layer selected from an l-type oxide thin film layer and a (100) oriented spinel oxide thin film layer.

In the above structure, the (100) -oriented NaCl-type oxide thin-film layer and the (100) -oriented spinel-type oxide thin-film layer are disposed between the lower electrode and the perovskite-type dielectric thin-film layer. It is preferred to have at least one selected layer.

In the above structure, the perovskite-type dielectric thin film is made of (Ba _1-x Sr _x ) TiO ₃ (0 ≦ x
≦ 1.0) or Pb ｛(Mg _1/3 , Nb _2/3 ) _1-y T
It is preferable that i _y ｝ O ₃ (0 ≦ y ≦ 1.0).

In the above structure, the NaCl-type oxide thin film is preferably at least one selected from a magnesium oxide thin film, a cobalt oxide thin film, and a nickel oxide thin film.

In the above structure, the spinel oxide thin film is preferably an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component.

In the above structure, a lower electrode is formed directly on the non-electrode substrate, a (100) -oriented NaCl oxide thin film is formed thereon, and a (10)
Preferably, a perovskite-type dielectric thin film layer oriented on the 0) plane is formed, and an upper electrode is formed thereon.

In the above structure, the lower electrode is formed directly on the non-electrode substrate, a (100) oriented spinel-type oriented thin film layer is formed thereon, and (1)
(00) An oriented NaCl-type oxide thin film is formed,
It is preferable that a perovskite-type dielectric thin film layer oriented in the (100) plane is formed thereon, and an upper electrode is formed thereon.

In the above structure, a (100) oriented NaCl type oxide thin film is formed on a non-electrode substrate, a lower electrode is formed thereon, and a (100)
It is preferable that an oriented perovskite type dielectric thin film layer is formed on the surface, and an upper electrode is formed thereon.

In the above structure, a (100) oriented spinel oxide thin film is formed on the non-electrode substrate, a lower electrode is formed thereon, and a (100)
It is preferable that an oriented perovskite type dielectric thin film layer is formed on the surface, and an upper electrode is formed thereon.

Next, according to the method for manufacturing a thin film capacitor of the present invention, a lower electrode is formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, and a dielectric thin film layer is directly or indirectly formed thereon. The upper electrode is formed directly or indirectly thereon, and the two electrodes are formed by sputtering, vacuum deposition, CVD, and plasma CV.
A method for manufacturing a thin film capacitor formed by using at least one method selected from the method D, wherein a lower surface or an upper surface of the lower electrode is formed by a plasma CVD method (1).
00) oriented NaCl-type oxide thin film layer and (10)
At least one layer selected from a spinel-type oriented thin film layer oriented in (0) is formed, and a perovskite-type dielectric thin film layer oriented in the (100) plane is formed below the upper electrode by a plasma CVD method. It is characterized by doing.

In the above-mentioned structure, NaC oriented to (100) is formed on the lower electrode by a plasma CVD method.
It is preferable to form at least one layer selected from an l-type oxide thin film layer and a (100) oriented spinel oxide thin film layer, and then form a perovskite dielectric thin film layer thereon.

In the above structure, the perovskite type dielectric thin film is made of (Ba _{1 -x} Sr _x ) TiO ₃ (0 ≦ x
≦ 1.0) or Pb ｛(Mg _1/3 , Nb _2/3 ) _1-y T
It is preferable that i _y ｝ O ₃ (0 ≦ y ≦ 1.0).

In the above structure, the NaCl-type oxide thin film is preferably at least one selected from a magnesium oxide thin film, a cobalt oxide thin film and a nickel oxide thin film.

In the above structure, the spinel oxide thin film is preferably an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component.

[0022]

According to the structure of the present invention described above, a lower electrode is formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, and a dielectric thin film layer is formed thereon directly or indirectly. A thin film capacitor having an upper electrode directly or indirectly formed thereon, wherein the dielectric thin film layer is a perovskite type dielectric thin film layer oriented in a (100) plane, and the dielectric thin film By having at least one layer selected from a NaCl-type oxide thin film layer oriented to (100) and a spinel-type oxide thin film layer oriented to (100) in any part below the layer, A thin-film capacitor exhibiting high crystallinity and orientation can be obtained at a low cost from the beginning of the film, and a thin-film capacitor that can be reduced in size and increased in capacity can be realized. That is, it is possible to reduce or eliminate the deterioration of the characteristics due to the initial layer existing at the initial stage of the film formation of the dielectric thin film layer. This is influenced by the crystal arrangement of the NaCl-type oxide base film or the spinel-type oxide base film preferentially oriented to (100) or the platinum base film oriented to (100) formed on these oxide thin films, This is because a dielectric thin film having good crystallinity can be formed from the initial stage of film formation. In addition, by using plasma CVD as a method for forming a NaCl-type oxide thin film or a spinel-type oxide thin film as a base film, a (100) oriented film can be obtained regardless of the type of the base substrate. That is, it is not necessary to use an expensive single crystal substrate. Furthermore, by using plasma CVD as a method of forming a dielectric thin film, it is possible to form a film over a large area at a high speed, and therefore, compared with a case where a conventional film forming method such as a sputtering method or a CVD method is used. The time required for manufacturing can be greatly reduced, and the cost can be reduced.

In the above, the thickness of the perovskite type dielectric thin film layer is preferably 0.1 to 3 μm, and the thickness of the NaCl type oxide thin film layer and the spinel type oxide thin film layer is 20 nm.
A thickness of ３3 μm is preferred.

As a preferable example in the above, (10) is provided between the lower electrode and the perovskite type dielectric thin film layer.
0) oriented NaCl-type oxide thin film layer and (10)
At least one layer selected from the spinel-type oxide thin film layers oriented in 0) can be present.

As a preferred example in the above,
As a lobskite-type dielectric thin film, (Ba_1-xSr_x)
TiO_Three(0 ≦ x ≦ 1.0) or Pb ｛(Mg_1/3,
Nb _2/3)_1-yTi_y｝ O_ThreeUse (0 ≦ y ≦ 1.0)
it can.

As a preferable example in the above, N
magnesium oxide thin film as an aCl type oxide thin film,
At least one selected from a cobalt oxide thin film and a nickel oxide thin film can be used.

As a preferred example in the above, an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component can be used as the spinel oxide thin film.

As a preferable example in the above, the lower electrode is formed directly on the non-electrode substrate, and (10
A structure in which a NaCl-type oxide thin film oriented in (0) is formed, a perovskite-type dielectric thin film layer oriented in (100) plane is formed thereon, and an upper electrode is formed thereon.

As a preferable example in the above, the lower electrode is formed directly on the non-electrode substrate, and (10
0) to form a spinel-type oriented thin film layer oriented in
A structure in which a (100) -oriented NaCl oxide thin film is formed thereon, a (100) -oriented perovskite-type dielectric thin film layer is formed thereon, and an upper electrode is formed thereon. Can be adopted.

As a preferable example in the above, a (100) oriented NaCl type oxide thin film is formed on a non-electrode substrate, a lower electrode is formed thereon, and a (100) plane is oriented on the lower electrode. A structure in which a perovskite type dielectric thin film layer is formed and an upper electrode is formed thereon can be adopted.

As a preferable example in the above, a (100) oriented spinel oxide thin film is formed on a non-electrode substrate, a lower electrode is formed thereon, and a (100) plane is oriented thereon. A structure in which a perovskite type dielectric thin film layer is formed and an upper electrode is formed thereon can be adopted.

Next, according to the structure of the method for manufacturing a thin film capacitor of the present invention, the thin film capacitor can be efficiently and rationally manufactured. As an example in the above, at least one selected from a NaCl-type oxide thin film layer oriented to (100) and a spinel-type oxide thin film layer oriented to (100) on the lower electrode by a plasma CVD method. After forming a layer, a perovskite type dielectric thin film layer can be formed thereon.

In the above description, as an example, the perovskite type dielectric thin film is made of (Ba _1-x Sr _x ) TiO ₃ (0
≦ x ≦ 1.0) or Pb ｛(Mg _1/3 , Nb _2/3 )
It is preferable that _1-y Ti _y ｝ O ₃ (0 ≦ y ≦ 1.0) to obtain high orientation from the beginning of film formation.

As an example in the above, when the NaCl type oxide thin film is at least one selected from a magnesium oxide thin film, a cobalt oxide thin film and a nickel oxide thin film, it is possible to obtain high orientation from the initial stage of film formation. Preferred.

As an example in the above, when the spinel-type oxide thin film is an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component, high orientation can be obtained from the initial stage of film formation. Preferred for.

[0036]

The present invention will be described more specifically with reference to the following examples. (Example 1) In FIG. 1, a platinum film 2 as a metal electrode was provided on a Si substrate 1, and (10)
0) NiO as NaCl-type oxide thin film oriented in plane
A film 3 is provided. On this NiO film 3, Ba _0.7 Sr as a perovskite type dielectric thin film oriented in the (100) plane.
_{A 0.3} TiO ₃ film 4 is provided, and a platinum film 5 as a metal electrode is further provided.

In FIG. 2, inside the reaction chamber 6,
Electrode 7 built into substrate heater with substrate rotation mechanism 12
And an electrode 8 to which a high-frequency power supply (13.56 MHz) 9 is connected, is provided opposite to the electrode 7, and an electrode 7 is provided, and a base substrate 10 such as a Si wafer 1 on which a platinum film 2 is formed as a metal electrode is provided below the electrode 8. Have been. Further, an exhaust system 11 for keeping the reaction chamber 6 at a low pressure is provided on a side surface of the reaction chamber 6.
Is provided.

On the other hand, vaporizers 13, 14, 1 containing raw materials
5, 16, 17, 18 are valves 19, 20, 21, 22,
2, 23, and 24 are connected to an argon cylinder 31 of a carrier gas.
Opening and closing 8, 29, 30 controls the introduction of the source gas and the carrier gas into the reaction chamber 6. The oxygen cylinder 32 is provided in the base substrate 10 (Si having a platinum film formed thereon).
It is connected to a pipe opening between the substrate 8 and the electrode 8.

Here, the thin film capacitor in the first embodiment
A method of manufacturing the device will be described. First, rf is placed on a Si substrate.
100nm Pt film by magnetron sputtering system
To achieve. Sputtering conditions were: plasma power 50 W, substrate
Temperature 600 ° C, gas pressure 1.4Pa, sputtering time 14 minutes
It is. Next, the Si substrate (Pt film) on which this Pt film is formed
/ Si substrate) on the basis of the plasma CVD apparatus shown in FIG.
Attached to electrode 7 built in plate heater, heated to 600 ° C
After that, the NaCl oxide thin film and the perovskite type
An electric thin film is formed. Below, N by plasma CVD
aCl oxide thin film and perovskite type dielectric thin film
The fabrication will be described in detail. As a starting material, β-di
Nickel acetylacetonate of ketone metal complex @N
i (acac) _Two・ H_Two0, acac = C_FiveH₇O_Two},barium
Dipivaloylmethane @ Ba (DPM)_Two, DPM = C₁₁
H₁₉O_Two｝, Strontium dipivaloyl methane ｛Sr
(DPM)_Two｝ And tetraisopropoxy titanium ｛T
i (C_ThreeH₇O)_Four｝ Was used. Plasma CVD of FIG.
Nickel evaporator 17 in the device
Cetyl acetonate, barium dipivaloy in vaporizer 13
Methane, strontium dipivaloylme
Tan, tetraisopropoxytitanium into vaporizer 15
To 160 ° C, 235 ° C, 240 ° C, and 40 ° C, respectively.
Heat and hold. Open valves 23 and 29 and open argon
Nickel acetyl alcohol with carrier (20 SCCM flow rate)
Settonate vapor and oxygen as reaction gas (flow rate 10 SC
CM) in the reaction chamber 6 where the pressure is reduced by the exhaust system 11.
To generate plasma (power 1.4 W / cm^Two) Sa
And react for 1 minute under reduced pressure (5 Pa).
NiO film on heated base substrate (120 rotations / minute) 10
Was deposited to a thickness of 20 nm, and valves 23 and 29 were closed.

Further, while maintaining the vacuum, the valve 1
9, 20, 21, 25, 26 and 27 are opened, and the carrier gas (flow rate 25, 2 is supplied to the vaporizers 13, 14, 15 respectively).
5, 5 SCCM) to convert the vapors of barium dipivaloylmethane, strontium dipivaloylmethane and tetraisopropoxytitanium into oxygen (flow rate 10
SCCM) into the reaction chamber 6 and in a plasma (power 1.4 W / cm ² ) under reduced pressure (7 Pa) for 16 minutes.
In carrying out the reaction, the Ba _1-X Sr _X TiO ₃ layer was 2μm formed on the NiO film to prepare a _{Ba 1-X Sr X TiO 3} / NiO film. Then, the base substrate on which Ba _1-x Sr _x TiO ₃ / NiO was formed was taken out of the vacuum chamber, and a counter electrode (platinum film) was formed to a thickness of 100 nm by sputtering.
A thin film capacitor (sample number 1-a) was produced. The sputtering conditions were as follows: plasma power 50 W, substrate temperature 600 ° C.
The gas pressure is 1.5 Pa and the sputtering time is 15 minutes.

Further, for comparison, Si was formed by sputtering.
A thin film capacitor in which a Ba _1-x Sr _x TiO ₃ film was directly formed by a plasma CVD method without forming a NiO film on a platinum film formed on a substrate and a counter electrode (platinum) was formed by a sputtering method (sample No. 1-b) was prepared.

When the film composition was analyzed using an electron beam microanalyzer, the dielectric layer of each of the thin film capacitors (1-a) and (1-b) was Ba _0.7 Sr _0.3 TiO.
_{Was 3} .

The relative permittivity and dielectric loss (1 kHz, 1 V) of the thin film capacitors (1-a) and (1-b) at room temperature measured by the LCR meter were 4200, 1. 4%, and the thin film capacitors (1-b) were 2800 and 1.8%, respectively.
Met. Insulation resistance is thin film capacitor (1-a), (1
-B) Both were 10 ⁹ Ω · cm or more. The DC breakdown voltage of the thin film capacitor (1-a) was 1.8 MV / cm,
The value of the thin film capacitor (1-b) was 1.4 MV / cm.

Next, on the platinum film formed on the Si substrate,
Under the above film forming conditions in this film forming method, NiO film, Ba
_0.7Sr_0.3TiO_ThreeMembrane, Ba_0.7Sr_0.3TiO_Three/
A NiO film is formed and reflection high-energy electron diffraction (RHEED)
Analysis of crystal structure and crystal orientation by X-ray and X-ray diffraction
went. As a result, the NiO film is oriented in the (100) plane.
Was. Then, a NiO (100) oriented film is used as a base film.
By using, Ba _0.7Sr_0.3TiO_Three/ NiO
Ba in the membrane_0.7Sr_0.3TiO_ThreeLayer directly on the substrate
Shows a strong (100) orientation as compared with the case where
In addition, the crystallinity was significantly improved.

Using a high-resolution scanning electron microscope, B
The fracture surface and the surface of the a _0.7 Sr _0.3 TiO ₃ / NiO film were observed. As a result, the Ba _0.7 Sr _0.3 TiO ₃ layer was very dense and had a particle size of about 0.20 μm.

When a Co oxide film or a Mg oxide film is used as the NaCl type oxide film in addition to the above-mentioned Ni oxide,
Ba _1-x Sr _x TiO ₃ with different composition as dielectric thin film
When a film is used, Pb や (Mg _1/3 , Nb _2/3 ) _1-y
Similarly, even when a Ti _y O ₃ film is used, better characteristics are exhibited by using the above NaCl-type oxide film as the underlayer as compared with a case where a dielectric thin film is directly formed on an electrode. A thin film capacitor was obtained. Representative results are shown in Table 1.

[0047]

[Table 1]

As a starting material, a NaCl type oxide film was used.
Was prepared using a β-diketone metal complex. Perovs
To manufacture a kite-type dielectric thin film, Ba (D
PM)_TwoSr (DPM) for strontium source_Two, Chita
Ti (C)_ThreeH₇O)_FourAnd Ti (DPM)_Two・
(C_ThreeH₇O)_TwoPb (DPM) for lead source_TwoAnd Pb
(C_TwoH_Five)_Four, Mg (DPM) for magnesium source_TwoYou
And Mg (acac) _Two, Nb (C_TwoH
_FiveO)_FiveAnd Nb (DPM)_Two・ Cl_ThreeWas used.

Further, when a metal material other than Pt, for example, nickel, palladium, silver / palladium alloy, copper, or the like is used as the metal electrode, a sputtering method, a vacuum deposition method, a CVD method, It was confirmed that a thin film capacitor exhibiting the same characteristics can be obtained by using any of the CVD methods.

(Embodiment 2) In FIG.
Above, a platinum film 36 as a metal electrode is provided, on the platinum film 36 is provided with Ni _{0. 5} Fe _2.5 O ₄ film 37 as a spinel type oxide thin film oriented in the (100) plane, the N
Ba _0.8 Sr _0.2 as a perovskite type dielectric thin film oriented on the (100) plane on the i _0.5 Fe _2.5 O ₄ film 37
A TiO ₃ film 38 is provided, and a platinum film 39 as a metal electrode is further provided.

Here, the thin film capacitor in the second embodiment
A method of manufacturing the device will be described. First, on a Si substrate, r
100 nm of Pt film by f magnetron sputtering device
Form. Sputtering conditions were as follows: plasma power 50 W, base
Plate temperature 600 ° C, gas pressure 1.4Pa, sputtering time 14
Minutes. Next, the Si substrate (Pt
Film / Si substrate) of the plasma CVD apparatus shown in FIG.
Attached to the electrode 7 inside the substrate heater,
After heating, spinel oxide thin film and perovskite
Form a dielectric thin film. Here, plasma CVD is used.
NaCl oxide thin film and perovskite type dielectric thin film
The fabrication of the film will be described in detail. Β-di as starting material
Nickel acetylacetonate of ketone metal complex @N
i (acac) _Two・ H_Two0, acac = C_FiveH₇O_Two｝, Iron acetylene
Ruacetonate @Fe (acac)_Three｝, Barium dipivaloy
Lumethane @ Ba (DPM)_Two, DPM = C₁₁H
₁₉O_Two｝, Strontium dipivaloyl methane ｛Sr
(DPM)_Two｝ And tetraisopropoxy titanium ｛T
i (C_ThreeH₇O)_Four｝ Was used.

In the plasma CVD apparatus shown in FIG. 2, nickel acetylacetonate subjected to dehydration treatment to the vaporizer 17, iron acetylacetonate to the vaporizer 18, and the vaporizer 13
Into the vaporizer 14, strontium dipivaloylmethane into the vaporizer 14, and tetraisopropoxytitanium into the vaporizer 15, 160 ° C, 130 ° C, respectively.
Heat and hold at 235 ° C, 235 ° C, and 40 ° C. Open valves 23, 24, 29 and 30 and open an argon carrier (flow rate 20 SCCM, 30 SCC for vaporizers 17 and 18 respectively).
M) together with the vapor of nickel acetylacetonate, the vapor of iron acetylacetonate, and oxygen (flow rate 15 SCCM) as a reaction gas into the reaction chamber 6 depressurized by the exhaust system 11 to generate plasma (power 1.4 W).
/ Cm ² ) and react under reduced pressure (5 Pa) for 2 minutes.
The Ni ^x Fe ^3-x O ₄ film was 50nm deposited on the underlying substrate (120 rev / min) 10 heated to 550 ° C., the valve 2
3, 24, 29 and 30 were closed.

Further, while maintaining the vacuum, the valve 1
Open 9,20,21,25,26,27 and
(The flow rate is 25, 3 for the vaporizers 13, 14, 15, respectively.)
0,5 SCCM), barium dipivaloylmethane,
Trontium dipivaloylmethane｝ and tetraisop
The vapor of ropoxytitanium is converted to oxygen (flow rate 10
SCCM) and plasma into the reaction chamber 6
Medium (power 1.4W / cm^Two) For 15 minutes under reduced pressure (7Pa)
And react with Ni^xFe^3-xO_FourBa on the membrane_{1- X}Sr
_XTiO_ThreeA film having a thickness of 1.6 μm was formed, and Ba was formed._1-XSr_XTi
O_Three/ Ni_XFe _3-XO_FourA film was prepared. And Ba
_1-XSr_XTiO_Three/ Ni_XFe_3-xO_FourUnder the formed
Remove the ground substrate from the vacuum chamber and
100nm counter electrode (platinum film)
A sensor (sample number 2-a) was produced. The sputtering conditions are
Plasma power 60W, substrate temperature 550 ° C, gas pressure 2P
a, The deposition time is 15 minutes.

For comparison, Si was also used for sputtering.
A Ba _1-x Sr _x TiO ₃ film is directly formed by a plasma CVD method without forming a Ni _x Fe _3-x O ₄ film on a platinum film formed on a substrate, and a counter electrode (platinum) is formed by a sputtering method. The formed thin film capacitor (sample number 2-b) was produced.

When the film composition was analyzed by an electron beam microanalyzer, the underlayer of the thin film capacitor (2-a) was Ni _0.5 Fe _2.5 O ₄ and the thin film capacitor (2-a)
And the dielectric layers of (2-b) are both Ba _0.8 Sr
_0.2 TiO ₃ .

The relative permittivity and dielectric loss (1 kHz, 1 V) of the thin film capacitors (2-a) and (2-b) at room temperature measured by the LCR meter were 3100, 2. 0%, and the values of the thin film capacitors (2-b) were 2800 and 2.9%, respectively. The insulation resistance of the thin film capacitors (2-a) and (2-
b) Both were 10 ⁹ Ω · cm or more. The DC breakdown voltage was 1.7 MV / cm for the thin film capacitor (2-a) and 1.2 MV / cm for the thin film capacitor (2-b).

Next, on a platinum film formed on a Si substrate, Ni _0.5 Fe _2.5
O ₄ film, Ba _0.8 Sr _0.2 TiO ₃ film, Ba _0.8 Sr
_{A 0.2} TiO ₃ / Ni _0.5 Fe _2.5 O ₄ film was formed, and the crystal structure and crystal orientation were analyzed by reflection high-energy electron diffraction (RHEED) and X-ray diffraction. As a result, Ni _0.
5 Fe _2.5 O ₄ film was oriented in the (100) plane. By using the Ni _0. of ₅ Fe _2.5 O ₄ (100) oriented film as a base film, Ba _0.8 Sr _0.2 TiO ₃ /
The Ba _0.8 Sr _0.2 TiO ₃ layer in the NiO film showed strong (100) orientation and significantly improved crystallinity as compared with the case where it was formed directly on the substrate.

Using a high-resolution scanning electron microscope, B
a_0.8Sr_0.2TiO_Three/ Ni_0.5Fe_2.5O_FourMembrane rupture
The cross section and surface were observed. As a result, Ba_0.8Sr_0.2T
iO _ThreeThe layer is very dense with a particle size of about 0.22 μm.
Was.

As a spinel-type oxide film, a film having a composition other than the above, a Ba _1-x Sr _x TiO ₃ film having a different composition as a dielectric thin film, or Pb ｛(M
g _1/3, Nb _2/3) also in _1-y Ti _y O ₃ if the membrane using, manufactured by using the spinel-type oxide film as an underlying layer, a dielectric thin film directly on the electrode As a result, a thin film capacitor showing better characteristics was obtained. Representative results are shown in Table 2.

[0060]

[Table 2]

As a starting material, a spinel oxide film
Was prepared using a β-diketone metal complex. Perovs
To manufacture a kite-type dielectric thin film, Ba (D
PM)_TwoSr (DPM) for strontium source_Two, Chita
Ti (C)_ThreeH₇O)_FourAnd Ti (DPM)_Two・
(C_ThreeH₇O)_TwoPb (DPM) for lead source_TwoAnd Pb
(C_TwoH_Five)_Four, Mg (DPM) for magnesium source_TwoYou
And Mg (acac) _Two, Nb (C_TwoH
_FiveO)_FiveAnd Nb (DPM)_Two・ Cl_ThreeWas used.

Further, when a metal material other than Pt, for example, nickel, palladium, silver / palladium alloy, copper, or the like is used as the metal electrode, a sputtering method, a vacuum deposition method, a CVD method, It was confirmed that a thin film capacitor exhibiting the same characteristics can be obtained by using any of the CVD methods.

(Embodiment 3) In FIG.
A NaCl-type oxide thin film oriented on the (100) plane
A NiO film 42 is provided on the
A platinum film 43 as an electrode is provided, and on this platinum 43,
A perovskite-type dielectric thin film oriented on a (100) plane;
Ba_0.5Sr_0.5TiO_ThreeProviding a film 44,
A platinum film 45 as a metal electrode is provided. Implemented here
A method for manufacturing the thin film capacitor in Example 3 will be described.
You. The vaporizer 17 in the plasma CVD apparatus of FIG.
Nickel acetylacetonate with water treatment, vaporizer
13 is barium dipivaloylmethane, and vaporizer 14 is
Rontium dipivaloylmethane, Tetri for vaporizer 15
Sopropoxy titanium was added, and the temperature was 160 ° C and 235, respectively.
C., 240.degree. C. and 40.degree. Valve 2
Open 3, 29 and with argon carrier (flow rate 20 SCCM)
The vapor of nickel acetylacetonate and the reaction gas
Oxygen (flow rate 10 SCCM) is reduced by the exhaust system 11.
Into the reaction chamber 6 and generate plasma (electrode
Power 1.4W / cm ^Two) For 3 minutes under reduced pressure (5 Pa)
The substrate was heated to 600 ° C (120 rotations /
Minute) A NiO film is formed to a thickness of 60 nm on
29 was closed. The NiO film / Si substrate was cooled to room temperature
After that, take out platinum with rf magnetron sputtering device.
A thin film was formed on the NiO film. Sputtering conditions are plasma
40 W, gas pressure 1.0 Pa, substrate temperature 600 ° C., film formation
The time is 20 minutes. The thickness of the Pt film is 80 nm.
You.

Then, the Pt film / NiO film / Si substrate is cooled to room temperature and taken out.
The Pt film / NiO film / Si substrate was set at 600
Heat to ° C. Pt film / NiO film / Si substrate is 600 ℃
After heating to 19,20,21,25,2
6 and 27, open the carrier gas (vaporizer 13, 14, 1
5, vapors of barium dipivaloylmethane, strontium dipivaloylmethane｝ and tetraisopropoxytitanium are introduced into the reaction chamber 6 together with oxygen (flow rate of 10 SCCM) at a flow rate of 25, 3030 and 5 SCCM, respectively. And in plasma (power 1.4W / c
m ² ) for 15 minutes under reduced pressure (7 Pa).
A 2.2 μm Ba _{1- x} Sr _x TiO ₃ film is formed on the film,
To prepare a _{Ba 1-x Sr x TiO 3} / Pt / NiO film.
Then, the Si substrate on which the Ba _1-x Sr _x TiO ₃ / Pt / NiO film was formed was taken out of the vacuum chamber, a counter electrode (platinum film) was formed to a thickness of 100 nm by sputtering, and a thin film capacitor (sample number 3-a) was formed. Produced. The sputtering conditions are plasma 50 W, gas pressure 1.4 Pa, substrate temperature 600 ° C., and film formation time 15 minutes.

For comparison, a Pt film was directly formed on a Si substrate by sputtering without forming a NiO film, and a Ba _1-x Sr _x TiO ₃ film was similarly formed on the Pt film by a plasma CVD method. Thus, a thin film capacitor (sample number 3-b) in which a counter electrode (platinum) was formed by a sputtering method was produced.

Electron beam micro analyzer (EPMA)
Thin film capacitors (3-a) and (3-a)
The composition of the dielectric layer of b) was Ba _0.5 Sr _0.5 TiO ₃ .

The relative permittivity and dielectric loss (1 kHz, 1 V) at room temperature of the thin film capacitors (3-a) and (3-b) measured by the LCR meter were 4000, 1. 7%, and the values of the thin film capacitors (3-b) were 2100 and 1.8%, respectively. The insulation resistance of the thin film capacitors (3-a), (3-
b) Both were 10 ⁹ Ω · cm or more. The DC breakdown voltage of the thin film capacitor (3-a) was 1.8 MV / cm, and that of the thin film capacitor (3-b) was 1.5 MV / cm.

Next, a NiO film, a Pt film, and a Pt / NiO film were formed on a Si substrate under the above film forming conditions in this film forming method.
Film, Ba _0.5 Sr _0.5 TiO ₃ film, Ba _0.5 Sr _0.5 T
An iO ₃ / Pt / NiO film was formed, and the crystal structure and the crystal orientation were analyzed by reflection high-energy electron diffraction (RHEED) and X-ray diffraction. As a result, the NiO film becomes (100)
It was oriented in the plane. The Pt film was non-oriented. And
By using the (100) oriented film of NiO as the underlayer, the Pt layer in the Pt / NiO film was oriented to (100). Further, by using a (100) oriented film of Pt as a base film, Ba _0.5 Sr _0.5 TiO ₃ / P
The Ba _0.5 Sr _0.5 TiO ₃ layer in the t / NiO film is
Stronger than when directly formed on a substrate (100)
In addition to showing the orientation, the crystallinity was also greatly improved.

Using a high-resolution scanning electron microscope, B
The fracture surface and the surface of the a _0.5 Sr _0.5 TiO ₃ / Pt / NiO film were observed. As a result, the Ba _0.5 Sr _0.5 TiO ₃ layer was very dense and had a particle size of about 0.2 μm.

When a Co oxide film or a Mg oxide film is used as the NaCl type oxide film in addition to the above Ni oxide,
Ba _1-x Sr _x TiO ₃ with different composition as dielectric thin film
When a film is used, Pb や (Mg _1/3 , Nb _2/3 ) _1-y
Similarly, in the case of using the Ti _y ｝ O ₃ film, better characteristics can be obtained by using the NaCl-type oxide film as the underlayer as compared with the case where the dielectric thin film is directly formed on the electrode. The thin film capacitor shown was obtained. Representative results are shown in Table 3.

[0071]

[Table 3]

As a starting material, a NaCl type oxide film was used.
Was prepared using a β-diketone metal complex. Perovs
To manufacture a kite-type dielectric thin film, Ba (D
PM)_TwoSr (DPM) for strontium source_Two, Chita
Ti (C)_ThreeH₇O)_FourAnd Ti (DPM)_Two・
(C_ThreeH₇O)_TwoPb (DPM) for lead source_TwoAnd Pb
(C_TwoH_Five)_Four, Mg (DPM) for magnesium source_TwoYou
And Mg (acac) _Two, Nb (C_TwoH
_FiveO)_FiveAnd Nb (DPM)_Two・ Cl_ThreeWas used.

Further, when a metal material other than Pt, for example, nickel, palladium, silver / palladium alloy, copper, or the like is used as the metal electrode, a sputtering method, a vacuum deposition method, a CVD method, It was confirmed that a thin film capacitor exhibiting the same characteristics can be obtained by using any of the CVD methods.

(Embodiment 4) Referring to FIG.
A Ni _0.5 Fe _2.5 O ₄ film 52 as a spinel-type oxide thin film oriented on the (100) plane is provided thereon.
Platinum film 5 as metal electrode on _0.5 Fe _2.5 O ₄ film 52
And a Ba _0.6 Sr as a perovskite-type dielectric thin film oriented on the (100) plane on the platinum film 53.
_{A 0.4} TiO ₃ film 54 is provided, and a platinum film 55 as a metal electrode is further provided.

Here, the thin film capacitor in the fourth embodiment
A method of manufacturing the device will be described. Β-diketo as starting material
Nickel acetylacetonate ン Ni (a
cac) _Two・ H_Two0, acac = C_FiveH₇O_Two｝, Iron acetyla
Settnerto Fe (acac)_Three｝, Barium dipivaloylme
Tan @ Ba (DPM)_Two, DPM = C₁₁H₁₉O_Two｝,
Trontium dipivaloylmethane @ Sr (DPM)_Two｝
And tetraisopropoxytitanium @ Ti (C_ThreeH
₇O)_Four｝ Was used.

In the plasma CVD apparatus shown in FIG. 2, the vaporizer 17 is dehydrated nickel acetylacetonate, the vaporizer 18 is iron acetylacetonate, and the vaporizer 13
Into the vaporizer 14, strontium dipivaloylmethane into the vaporizer 14, and tetraisopropoxytitanium into the vaporizer 15, 160 ° C, 130 ° C, respectively.
Heat and hold at 235 ° C, 235 ° C, and 40 ° C. Open valves 23, 24, 29 and 30 and open an argon carrier (flow rate 20 SCCM, 30 SCC for vaporizers 17 and 18 respectively).
M) together with the vapor of nickel acetylacetonate, the vapor of iron acetylacetonate, and oxygen (flow rate 15 SCCM) as a reaction gas into the reaction chamber 6 depressurized by the exhaust system 11 to generate plasma (power 1.4 W).
/ Cm ² ) and react under reduced pressure (5 Pa) for 4 minutes.
A Ni _x Fe _1-x O ₄ film is formed to a thickness of 90 nm on a base substrate (120 rotations / minute) 10 heated to 550 ° C.
3, 24, 29 and 30 were closed.

The Si substrate on which the Ni _x Fe _{1 -x} O ₄ film was formed was cooled to room temperature, taken out, and a platinum thin film was formed on the Ni ^x Fe ^{3 -x} O ₄ film using an rf magnetron sputtering apparatus. The sputtering conditions were as follows: plasma 40 W, gas pressure 1.
0 Pa, the substrate temperature is 600 ° C., and the film formation time is 25 minutes. Note that the thickness of the Pt film is 100 nm.

Then, Pt / Ni^xFe^3-xO_FourShape the membrane
After removing the formed Si substrate to room temperature, take out plasma
Attached on the electrode 7 of the CVD device, the exhaust system 11
The pressure inside the reaction chamber is reduced and heated to 600 ° C.
You. Pt / Ni^xFe^3-xO _FourThe Si substrate with the film formed
After heating to 600 ° C., valves 19, 20, 21,
25, 26, 27, and open the carrier gas (vaporizer 13,
14 and 15 according to flow rate 25, 30, 5 SCCM)
Barium dipivaloylmethane, strontium dipi
Valoylmethane and tetraisopropoxytitanium
The steam is reacted with oxygen (flow rate 10 SCCM) as a reaction gas.
Into the reaction chamber 6 and in plasma (power 1.4 W).
/cm^Two) For 15 minutes under reduced pressure (7 Pa).
t / Ni_xFe_1-xO_FourBa on the membrane_1-xSr_xTiO_Three
A film of about 1.9 μm is formed and Ba_1-xSr_xTiO_Three/ P
t / Ni^xFe^3-xO_FourA film was prepared. And Ba
_1-xSr_xTiO_Three/ Pt / Ni^xFe^3-xO_FourForm
Removed Si substrate from vacuum chamber
A 100 nm counter electrode (platinum film) is formed by the
A capacitor (sample number 4-a) was produced. Sputtering strip
The conditions were plasma 50W, gas pressure 1.4Pa, substrate temperature 6
00 ° C., film formation time 15 minutes.

For comparison, Pt / N on Si substrate
i ^x Fe ^3-x O ₄ directly without making a film Ba _1-x Sr x T
Similarly, a thin film capacitor (sample number 4-b) in which an iO ₃ film was formed by a plasma CVD method and a counter electrode (platinum) was formed by a sputtering method.

Electron beam micro analyzer (EPMA)
Thin film capacitors (4-a) and (4-a)
The composition of the dielectric layer of b) is Ba _0.6 Sr _0.4 Ti
O ₃ . The composition of the spinel oxide thin film of the thin-film capacitor (4-a) was Ni _0.5 Fe _2.5 O ₄ .

The relative permittivity and dielectric loss (1 kHz, 1 V) at room temperature of the thin film capacitors (4-a) and (4-b) measured by the LCR meter were 4100, 1. 8%, and the values of the thin film capacitors (4-b) were 2100 and 1.8%, respectively. The insulation resistance of the thin film capacitors (4-a), (4-
b) Both were 10 ⁹ Ω · cm or more. The DC breakdown voltage was 1.7 MV / cm for the thin film capacitor (2-a) and 1.2 MV / cm for the thin film capacitor (2-b).

Next, in this film forming method on a Si substrate,
Under the above film forming conditions, Ni_0.5Fe_2.5O_FourFilm, Pt film, B
a_0.6Sr_0.4TiO_ThreeMembrane, Ba_0.6Sr_0.4TiO_Three
/ Pt / Ni_0.5Fe_2.5O_FourA film is formed and reflected high-speed electricity
Crystal structure by proton diffraction (RHEED) and X-ray diffraction
And analysis of crystal orientation was performed. As a result, Ni_0.5Fe
_2.5O_FourThe film was oriented in the (100) plane. Pt film
Was non-oriented. Then, Pt (10
0) By using an alignment film, Ba_0.6Sr _0.4Ti
O_Three/ Pt / Ni_0.5Fe_2.5O_FourBa in the membrane_0.6
Sr_0.4TiO _ThreeThe layer is different from the one formed directly on the substrate.
By comparison, it shows a strong (100) orientation and
Had also improved significantly.

Using a high-resolution scanning electron microscope, B
a _0.6 Sr _0.4 TiO ₃ / Pt / Ni _0.5 Fe _2.5 O ₄
The fracture surface and surface of the film were observed. As a result, Ba _0.6 Sr
_{The 0.4} TiO ₃ layer was very dense and had a particle size of about 0.22 μm.

As a spinel oxide film, a film having a composition other than the above is used, a Ba _1-x Sr _x TiO ₃ film having a different composition is used as a dielectric thin film, or Pb ｛(M
_{g 1/3, Nb 2/3)} 1-y Ti y} O 3 film also in the case of using, by using the above spinel-type oxide film as an underlying layer, a dielectric thin film directly on the electrode A thin-film capacitor showing better characteristics as compared with the case where it was manufactured was obtained. Representative results are shown in Table 4.

[0085]

[Table 4]

As a starting material, a β-diketone metal complex was used for producing a spinel type oxide film. To form a perovskite-type dielectric thin film, Ba (D) is used as a barium source.
_{PM) 2, Sr (DPM)} 2 in the strontium source, Ti (C ₃ H ₇ titanium source O) ₄ and Ti (DPM) ₂ ·
(C ₃ H ₇ O) ₂ , Pb (DPM) ₂ and Pb as lead sources
(C ₂ H ₅ ) ₄ , Mg (DPM) ₂ and Mg (acac) _{2 for} the magnesium source, and Nb (C ₂ H ₅ O) for the niobium source
₅ and Nb (DPM) ₂ · Cl ₃ were used.

Further, when a metal material other than Pt, for example, nickel, palladium, silver / palladium alloy, copper, or the like is used as the metal electrode, a sputtering method, a vacuum deposition method, a CVD method, It was confirmed that a thin film capacitor exhibiting the same characteristics can be obtained by using any of the CVD methods.

Example 5 In FIG. 6, a platinum substrate 61 as a metal electrode was provided, and (1)
Ni) as a NaCl-type oxide thin film oriented on the (00) plane
An O film 62 is provided, and Ba _0.7 as a perovskite type dielectric thin film oriented on the (100) plane is formed on the NiO film 62.
An Sr _0.3 TiO ₃ film 63 is provided, and a platinum film 64 as a metal electrode is further provided.

Here, a method of manufacturing the thin film capacitor in the sixth embodiment will be described. First, a platinum substrate (Pt film / Si substrate) was attached to the electrode 7 inside the substrate heater of the plasma CVD apparatus shown in FIG. 2, and after heating to 600 ° C., the NaCl oxide thin film and the perovskite type dielectric thin film were removed. Make it. The following describes N by plasma CVD.
The fabrication of the aCl oxide thin film and the perovskite dielectric thin film will be described in detail. As a starting material, nickel acetylacetonate of β-diketone-based metal complex {N
i (acac) ₂ · H ₂ 0, acac = C ₅ H ₇ O ₂ ｝, barium dipivaloylmethane ｛Ba (DPM) ₂ , DPM = C ₁₁
H ₁₉ O ₂ }, strontium dipivaloylmethane {Sr
(DPM) ₂ } and isopropoxy titanium {Ti (C
₃ H ₇ O) ₄ } was used. In the plasma CVD apparatus of FIG. 2, nickel acetylacetonate subjected to dehydration treatment in the vaporizer 17, barium dipivaloyl methane in the vaporizer 13, strontium dipivaloyl methane in the vaporizer 14,
Put isopropoxy titanium in the vaporizer 15 and add 1
Heat to 60 ° C, 235 ° C, 240 ° C, and 40 ° C and hold. The valves 23 and 29 are opened, and the vapor of nickel acetylacetonate and oxygen as a reaction gas (flow rate 10 SCCM) are discharged together with the argon carrier (flow rate 20 SCCM).
The reaction mixture was introduced into the reaction chamber 6 decompressed by the step 1 to generate plasma (power: 1.4 W / cm ² ), reacted for 1 minute under reduced pressure (5 Pa), and heated to 600 ° C. under the substrate (120 rotations / Min) A NiO film was formed to a thickness of 20 nm on 10 and the valves 23 and 29 were closed.

Further, without breaking the vacuum, the valve 1
9, 20, 21, 25, 26 and 27 are opened, and the carrier gas (flow rate 25, 2 is supplied to the vaporizers 13, 14, 15 respectively).
5,5 SCCM) to convert the vapors of barium dipivaloylmethane, strontium dipivaloylmethane｝ and isopropoxytitanium into oxygen as a reaction gas (flow rate 10 SCCM).
At the same time, the reaction is carried out in a plasma (power 1.4 W / cm ² ) under reduced pressure (7 Pa) for 16 minutes, and a Ba _1-x Sr _x TiO ₃ film is formed on the NiO film by 2 μm.
m to form a Ba _1-x Sr _x TiO ₃ / NiO film. Then, the underlying substrate formed with the _{Ba 1- X Sr X TiO 3 /} NiO removed from the vacuum chamber, the counter electrode (platinum layer) was 100nm formed by sputtering, to produce a thin film capacitor (Sample No. 6-a). The sputtering conditions are plasma power of 50 W, substrate temperature of 600 ° C., gas pressure of 1.5 Pa, and sputtering time of 15 minutes.

For comparison, Si was used for sputtering.
A thin film capacitor in which a Ba _1-x Sr _x TiO ₃ film was directly formed by a plasma CVD method without forming a NiO film on a platinum film formed on a substrate and a counter electrode (platinum) was formed by a sputtering method (sample No. 6-b) was prepared.

When the film composition was analyzed using an electron beam microanalyzer, the dielectric layers of both the thin film capacitors (6-a) and (6-b) were made of Ba _0.7 Sr _0.3 TiO.
_{Was 3} . .

The relative permittivity and dielectric loss (1 kHz, 1 V) of the thin film capacitors (6-a) and (6-b) at room temperature measured by the LCR meter were 4300, 1. 5%, and that of the thin-film capacitors (6-b) was 2700 and 1.9%, respectively. The insulation resistance of the thin film capacitors (6-a), (6-
b) Both were 10 ⁹ Ω · cm or more. The DC breakdown voltage of the thin film capacitor (6-a) was 1.9 MV / cm, and that of the thin film capacitor (6-b) was 1.6 MV / cm.

Next, on a platinum substrate, a NiO film, Ba _0.7 Sr _0.3 TiO
₃ film, Ba _0.7 Sr _0.3 TiO ₃ / NiO film is formed,
The crystal structure and crystal orientation were analyzed by reflection high-energy electron diffraction (RHEED) and X-ray diffraction. As a result N
The iO film was oriented in the (100) plane. By using a (100) oriented film of NiO as a base film,
Ba _0.7 Sr _0.3 TiO ₃ / Ba _0.7 in the NiO film
The Sr _0.3 TiO ₃ layer exhibited strong (100) orientation and significantly improved crystallinity as compared with the case where it was formed directly on the substrate.

Using a high-resolution scanning electron microscope, B
The fracture surface and the surface of the a _0.7 Sr _0.3 TiO ₃ / NiO film were observed. As a result, the Ba _0.7 Sr _0.3 TiO ₃ layer was very dense and had a particle size of about 0.20 μm.

When a Co oxide film or a Mg oxide film is used as the NaCl type oxide film in addition to the above-mentioned Ni oxide,
Ba _1-x Sr _x TiO ₃ with different composition as dielectric thin film
When a film is used, Pb や (Mg _1/3 , Nb _2/3 ) _1-y
Similarly, even when a Ti _y O ₃ film is used, better characteristics are exhibited by using the above NaCl-type oxide film as the underlayer as compared with a case where a dielectric thin film is directly formed on an electrode. A thin film capacitor was obtained. Na
Even when a spinel-type oxide thin film was used instead of the Cl-type oxide film, a thin-film capacitor exhibiting similarly good characteristics was obtained. Representative results are shown in Table 5.

[0097]

[Table 5]

As a starting material, a β-diketone-based metal complex was used for producing a NaCl type oxide film and a spinel type oxide thin film. To prepare a perovskite-type dielectric thin film, Ba (DPM) ₂ is used as a barium source, Sr (DPM) _{2 as} a strontium source, and Ti (C ₃ H ₇ O) as a titanium source.
₄ and Ti (DPM) ₂ · (C ₃ H ₇ O) ₂ , Pb (DPM) ₂ and Pb (C ₂ H ₅ ) _{4 for} the lead source, Mg (DPM) ₂ and Mg (acac) _{2 for} the magnesium source,
Nb (C ₂ H ₅ O) ₅ and Nb (DPM) as niobium sources
₂ · Cl ₃ was used.

It was also confirmed that a thin film capacitor having the same characteristics can be obtained even when a metal electrode material other than Pt, such as nickel, palladium, a silver / palladium alloy, or copper, is used as the metal electrode substrate.

FIG. 7 shows an example of an external view of a thin film capacitor. After manufacturing by the above method, the substrate was 3.3 mm × 1.6.
Cut to mm. Then, metal lead wires 75 are soldered on the respective electrodes, and the whole is molded with an epoxy resin 76. The capacitance of this capacitor was 100 pF. 7, reference numeral 71 denotes a metal electrode substrate (platinum substrate); 72, a NaCl-type oxide film or spinel-type oxide thin film; 73, a perovskite-type dielectric thin film; and 74, a metal electrode (platinum film).

[0101]

As described above, according to the present invention, a lower electrode is formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, and a dielectric thin film layer is formed thereon directly or indirectly. Is formed, on which the upper electrode is formed directly or indirectly, a thin film capacitor,
The dielectric thin film layer is a perovskite-type dielectric thin film layer oriented in the (100) plane, and (100) oriented Na is oriented in any portion below the dielectric thin film layer.
By having at least one layer selected from a Cl-type oxide thin film layer and a (100) -oriented spinel-type oxide thin film layer, a thin-film capacitor exhibiting high crystallinity and orientation can be obtained at an inexpensive stage from the beginning of film formation. Thus, a thin film capacitor that can be reduced in size and capacity can be realized.

Next, according to the structure of the method for manufacturing a thin film capacitor of the present invention, the thin film capacitor can be efficiently and rationally manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a thin-film capacitor according to a first embodiment of the present invention.

FIG. 2 is a schematic view showing a plasma CVD apparatus used for forming a base layer and a dielectric layer of the thin film capacitor according to one embodiment of the present invention.

FIG. 3 is a schematic sectional view showing a thin film capacitor according to a second embodiment of the present invention.

FIG. 4 is a schematic sectional view showing a thin-film capacitor according to a third embodiment of the present invention.

FIG. 5 is a schematic sectional view showing a thin-film capacitor according to a fourth embodiment of the present invention.

FIG. 6 is a schematic sectional view showing a thin film capacitor according to a fifth embodiment of the present invention.

FIG. 7 is a partially cutaway schematic view showing a thin film capacitor according to a fifth embodiment of the present invention.

[Explanation of symbols]

Reference Signs List 1 Si substrate 2 Metal electrode (platinum film) 3 NaCl-type oxide thin film (NiO film) 4 Perovskite-type dielectric thin film (Ba _0.7 Sr _0.3 T)
iO ₃ film) 5 metal electrode (platinum layer) 6 reaction chamber 7 substrate heater visceral electrode 8 electrodes 9 high frequency power source 10 substrate 11 exhaust system 12 substrate rotating mechanism 13 to 18 vaporizer 19 to 30 argon valve 31 the carrier gas Cylinder 32 Oxygen cylinder 35 Si substrate 36 Metal electrode (platinum film) 37 Spinel type oxide thin film (Ni _0.5 Fe _2.5 O
₄ films) 38 Perovskite dielectric thin film (Ba _0.8 Sr _0.2
TiO ₃ film) 39 Metal electrode (platinum film) 41 Si substrate 42 NaCl type oxide thin film (NiO film) 43 Metal electrode (platinum film) 44 Perovskite type dielectric thin film (Ba _0.5 Sr _0.5)
TiO ₃ film) 45 Metal electrode (platinum film) 51 Si substrate 52 Spinel type oxide thin film (Ni _0.5 Fe _2.5 O
₄ ) 53 Metal electrode (platinum film) 54 Perovskite dielectric thin film (Ba _0.6 Sr _0.4
TiO ₃ film 55 Metal electrode (platinum film) 61 Metal electrode (platinum substrate) 62 NaCl type oxide thin film (NiO film) 63 Perovskite type dielectric thin film (Ba _0.7 Sr _0.3
TiO ₃ film) 64 Metal electrode (platinum film) 71 Metal electrode substrate (platinum substrate) 72 NaCl type oxide film or spinel type oxide thin film 73 Perovskite type dielectric thin film 74 Metal electrode (platinum film) 75 Metal lead wire 76 Epoxy Resin (mold resin)

Continuation of front page (72) Inventor Ryoichi Takayama 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-63-281248 (JP, A) JP-A-2-260408 (JP) JP-A-3-110861 (JP, A) JP-A-2-199108 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01G 4/12-4/12 448 H01G 4/00-4/10 H01G 4/14-4/40 H01G 13/00-13/06

Claims (14)

(57) [Claims] 1. A lower electrode is formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, on which a dielectric thin film layer is formed directly or indirectly, and on which a direct or indirect dielectric thin film layer is formed. in a thin film capacitor upper electrode is formed, the dielectric thin layer is a perovskite dielectric thin layer oriented to (100) plane, and gold as the electrode
Between the metal or non-electrode substrate and the lower electrode, or
In any part between the pole and the dielectric thin film layer , (10
0) oriented NaCl-type oxide thin film layer and (10)
A thin film capacitor having at least one layer selected from 0) oriented spinel oxide thin film layers. 2. A method according to claim 1, wherein the lower electrode and the perovskite type dielectric thin film layer include at least one selected from a (100) oriented NaCl type oxide thin film layer and a (100) oriented spinel type oxide thin film layer. 2. The method according to claim 1, wherein the layer has one layer.
2. The thin film capacitor according to 1. 3. The method according to claim 1, wherein the perovskite type dielectric thin film is (Ba)
_1-x Sr _x ) TiO ₃ (0 ≦ x ≦ 1.0) or Pb
｛(Mg _1/3 , Nb _2/3 ) _1-y Ti _y ｝ O ₃ (0 ≦ y ≦
1.0). 4. The thin film capacitor according to claim 1, wherein the NaCl type oxide thin film is at least one selected from a magnesium oxide thin film, a cobalt oxide thin film, and a nickel oxide thin film. 5. The thin film capacitor according to claim 1, wherein the spinel-type oxide thin film is an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component. 6. A lower electrode is directly formed on a non-electrode substrate, a (100) -oriented NaCl-type oxide thin film is formed thereon, and a (100) -oriented perovskite-type dielectric is formed thereon. The thin film capacitor according to claim 1, wherein a thin film layer is formed, and an upper electrode is formed thereon. 7. A lower electrode is directly formed on a non-electrode substrate, a (100) oriented spinel-type oriented thin film layer is formed thereon, and a (100) oriented N is oriented thereon.
An aCl-type oxide thin film is formed, and a (100) -oriented perovskite-type dielectric thin film layer is formed thereon,
2. The thin film capacitor according to claim 1, wherein an upper electrode is formed thereon. 8. A perovskite-type dielectric thin film having a (100) -oriented NaCl-type oxide thin film formed on a non-electrode substrate, a lower electrode formed thereon, and a (100) -plane oriented thereon. The thin film capacitor according to claim 1, wherein a layer is formed, and an upper electrode is formed thereon. 9. A perovskite-type dielectric thin film having a (100) -oriented spinel-type oxide thin film formed on a non-electrode substrate, a lower electrode formed thereon, and a (100) -plane oriented thereon. The thin film capacitor according to claim 1, wherein a layer is formed, and an upper electrode is formed thereon. 10. A lower electrode is formed directly or indirectly on a metal substrate or a non-electrode substrate as an electrode, and a dielectric thin film layer is formed thereon directly or indirectly, and a direct or indirect dielectric layer is formed thereon. A method of manufacturing a thin film capacitor, wherein an upper electrode is formed, and the two electrodes are formed by using at least one method selected from a sputtering method, a vacuum deposition method, a CVD method, and a plasma CVD method, At least one layer selected from a NaCl type oxide thin film layer oriented to (100) and a spinel type oriented thin film layer oriented to (100) is formed on the lower or upper surface of the lower electrode by plasma CVD. Forming a perovskite-type dielectric thin film layer oriented in the (100) plane below the upper electrode by using a plasma CVD method. Method of manufacturing capacitor. 11. At least one selected from a NaCl-type oxide thin film layer oriented to (100) and a spinel-type oxide thin film layer oriented to (100) by using a plasma CVD method on the lower electrode. The method for manufacturing a thin film capacitor according to claim 10, wherein a layer is formed, and a perovskite type dielectric thin film layer is formed thereon. 12. The method according to claim 11, wherein the perovskite-type dielectric thin film is (B
a_1-xSr_x) TiO _Three(0 ≦ x ≦ 1.0) or Pb
｛(Mg_1/3, Nb_2/3)_1-yTi_y｝ O_Three(0 ≦ y ≦
1.0).
Construction method. 13. The method according to claim 10, wherein the NaCl-type oxide thin film is at least one selected from a magnesium oxide thin film, a cobalt oxide thin film, and a nickel oxide thin film. 14. The method according to claim 10, wherein the spinel oxide thin film is an oxide thin film containing at least one component selected from iron, cobalt and aluminum as a main component.