JPS61220288A - Heating resistor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat generating resistor, and more particularly to a thin film heat generating resistor formed by forming a resistive thin film as a functional element on the surface of a substrate.

Such a resistor is suitably used as an electric-thermal energy conversion element in various electronic or electric devices.

[Prior Art] Heating resistors conventionally used as relatively small electric-to-thermal energy conversion elements in electronic or electrical equipment include thin film types, thick film types, and semiconductor types. . Among these, thin-film types consume less power than other types and have relatively good thermal responsiveness, so their applications are gradually increasing.

The performance required of such a heating resistor is that it has good heat generation response to a predetermined electric signal, good thermal conductivity, and good heat resistance against its own heat generation. and that various types of durability (for example, durability against thermal history) are good.

However, in the conventional thin film type heat generating resistor, the above-mentioned performance is not necessarily satisfactory, and further improvement of the characteristics is desired.

[Object of the Invention] In view of the above-mentioned prior art, one of the objects of the present invention is
The first object is to provide a thin film heating resistor with improved thermal responsiveness.

Another object of the present invention is to provide a thin film heating resistor with improved thermal conductivity.

Still another object of the present invention is to provide a thin film heating resistor with improved heat resistance.

Another object of the present invention is to provide a thin film heating resistor with improved durability.

[Summary of the Invention] The above objects are achieved by a novel thin film heating resistor according to the present invention.

In the thin film heating resistor of the present invention, a functional thin film made of an amorphous material made of carbon atoms as a matrix and containing germanium atoms, l\\rogen atoms, and hydrogen atoms is formed on a substrate. A thin film is characterized in that germanium atoms, halogen atoms, and/or hydrogen atoms are distributed nonuniformly in the film thickness direction.

Hereinafter, the present invention will be explained in more detail with reference to the drawings.

FIG. 1 is a partial sectional view showing the structure of an embodiment of the heating resistor of the present invention.

In this figure, 2 is a base, and 4 is a thin film for realizing functionality, that is, resistance.

In the present invention, there is no particular restriction on the material of the base 2, but in practice, it has good adhesion with the functional thin film 4 formed on its surface, and is suitable for use under heat during the formation of the functional thin film 4 and during use. It is preferable that the functional thin film 4 has good durability against the heat generated, and the base 2 preferably has a higher electrical resistance than the functional thin film 4 formed on its surface. Depending on the purpose of use of the resistor, the base 2 can be made of a material with low thermal conductivity or a material with high thermal conductivity.

Examples of the substrate 2 used in the present invention include those made of inorganic materials such as glass, ceramics, and silicon, and those made of organic materials such as polyamide resin and polyimide resin.

In the present invention, the functional thin film 4 is made of an amorphous material having carbon atoms as its base material and containing germanium atoms, halogen atoms, and hydrogen atoms. F as a norogen atom,
C1, Br, I, etc. can be used, and these may be used alone or in combination.

As the halogen atom, F and C1 are particularly preferred.

Among them, F is preferable.

The content of germanium atoms in the functional thin film 4 is appropriately selected so as to obtain desired characteristics depending on the intended use of the resistor, and is preferably 0.0001 to 40 at.%, more preferably 0.0001 to 40 at.%. 0005 to 20 atomic%,
The preferred range is o, oot to lO atomic %.

The content of halogen atoms in the functional thin film 4 is appropriately selected depending on the intended use of the resistor so as to obtain desired characteristics, and is preferably o or oo.

1 to 30 atomic%, more preferably 0.0005 to 30%
It is 20 atom %, preferably o, oot to lO atom %.

The content of hydrogen atoms in the functional thin film 4 is appropriately selected so as to obtain desired characteristics depending on the purpose of use of the resistor, and is preferably o, oooi to 30 at %, more preferably 0. 0.0005 to 20 atom %, preferably 0.001 to 10 atom %.

The sum of the germanium atom content, halogen atom content, and hydrogen atom content in the functional thin film 4 is appropriately selected so as to obtain desired characteristics depending on the intended use of the resistor, but is preferably The content is 0.0001 to 40 atomic %, more preferably 0.0005 to 30 atomic %, and preferably 0.001 to 20 atomic %.

In the present invention, 4! The distribution of germanium atoms, halogen atoms, and/or hydrogen atoms in the functional thin film 4 is non-uniform in the film thickness direction in the functional thin film 4.

The content rate of halogen atoms and/or hydrogen atoms may be such that the content rate gradually increases from the side of the substrate 2 to the surface side, or conversely, the content rate may decrease. , /\The change in the content of rogen atoms and/or hydrogen atoms may be such that it has a maximum value or a minimum value in the thin film [li4].
The change in the content of germanium atoms, )\rogen atoms and/or hydrogen atoms in the film thickness direction is appropriately selected so as to obtain desired characteristics depending on the use of the heating resistor.

FIG. 2 to FIG. 7 show functional parts 1194 of the heating resistor of the present invention.
In these figures, the vertical axis represents the distance T in the film thickness direction from the interface with the substrate 2. , t represents the film thickness of the functional part 11g4, and the horizontal axis represents the content C of germanium atoms, halogen atoms, and/or hydrogen atoms. In each figure, the scale of the vertical axis T and the horizontal axis C is They are not necessarily uniform, but are varied to bring out the characteristics of each figure. Therefore, in actual application, various distributions are used for each diagram based on the differences in specific values.

In the heating resistor of the present invention, an amorphous material (hereinafter sometimes abbreviated as ra-C:Ge:(X,H)J) is formed of carbon as a matrix and contains germanium atoms, halogen atoms, and hydrogen atoms. Here, X represents a halogen atom,) a functional unit consisting of [! 4 is.

For example, it is formed by a plasma CVD method such as a glow discharge method, or a vacuum deposition method such as a sputtering method.

For example, a-C:Ge:(X
, H), basically, the substrate 2 is placed in a deposition chamber under reduced pressure, and a raw material gas for C supply and germanium that can supply carbon atoms (C) into the deposition chamber. A raw material gas for Ge supply that can supply atoms (Ge), a raw material gas for X supply that can supply halogen atoms (X), and a raw material gas for H supply that can supply hydrogen atoms (H) are introduced. At this time, while changing the introduced amounts of the Ge supply raw material gas, the X supply raw material gas, and/or the H supply raw material gas, a glow discharge is generated in the deposition chamber using high frequency waves or microwaves, and the surface of the substrate 2 is a-C:Ge:(X,H
) may be formed.

In addition, a-C:Ge:(X
, H), basically, the substrate 2 is placed in a deposition chamber under reduced pressure, and an inert gas such as Ar, He, etc. or a base gas of these gases is injected in the deposition chamber. When sputtering a target composed of C in a mixed gas atmosphere, a source gas for Ge supply, a source gas for X supply, and a source gas for H supply are introduced into the deposition chamber, and at this time, the amount introduced is Just change it.

In the above method, as the raw material gas for C supply, the raw material gas for Ge supply, the raw material gas for X supply, and the raw material gas for H supply, in addition to those in a gas state at room temperature and normal pressure, substances that can be gasified under reduced pressure are used. can be used.

Examples of raw materials for C supply include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, aromatic hydrocarbons, etc. The saturated hydrocarbons are methane (CH4) and ethane (C2H6).

Propane (C3Ha), n-butane (n-C4H1o)
, pentane (C5H12), ethylene hydrocarbons such as ethylene (C2H4), propylene (C3H6)
, butene-1 (C4H8), butene-2 (C4Hll
), inbutylene (C4Ha), pentene (C
s Hzo), acetylene hydrocarbons include acetylene (C2I2) and methylacetylene (C3H4).
, butyne (C4Ha), and aromatic hydrocarbons include benzene CCeHa).

Examples of raw materials for supplying Ge include GeH4, Ge2
H6, Ge3 HB, Ge4 H1□.

Ge5Hx2, Ge6 I14. Ge7)116.
GeB) fig, germanium hydride such as Ge9H2o.

G e F 4, (GeF2)s, (GeF2)a.

(GeF2)4, Ge2 F6, Ge3 FB
,G.

HF3, GeB2 F2, GeC14 (GeC12
)s, GeBr4, (GeBr2)s, Ge2 C16
, Ge2 CI3 F3, etc. (7) Germanium halides (halogenated water substituted with halogen atoms (IBM Conductor)).

Examples of raw materials for supplying X include halogens, halides, interhalogen compounds, halogen-substituted hydrocarbon derivatives, etc. Specifically, the halogens include F2, C12, and Br.
2, I2, HF, HC as halides
I, HBr, HI, BrF as an interhalogen compound,
CIF, ClF3, BrF5. BrF3. IF3. I
F7. ICI, IBr, halogen-substituted hydrocarbon '1g derivatives include CF4, CHF3, CH2F2, CH
3F, CCl4. CHCl3, CH2C12, CH3
Cl, CBr4. CHBr3. C)! 2Br2, CH3
Examples include Br, CI4, CHI3, CH2I2, CH3I, and the like.

Examples of raw materials for supplying H include hydrogen gas and hydrocarbons such as saturated hydrocarbons, ethylene hydrocarbons, acetylene hydrocarbons, and aromatic hydrocarbons, which are also the raw materials for supplying C.

These raw materials may be used alone or in combination.

In the above SS forming method, in order to control the amount of germanium atoms, the amount of halogen atoms, and the amount of hydrogen atoms contained in the thin film 4 to be formed, and the characteristics of the thin film 4, it is necessary to control the substrate temperature and the supply of source gas. The amount, discharge power, pressure inside the deposition chamber, etc. are set appropriately.

In particular, 1 feature 811 in which the distribution of germanium atoms, halogen atoms, and/or hydrogen atoms is uneven in the film thickness direction of the present invention
To obtain 14, germanium atoms into the deposition chamber,
It is preferable to change the amount of halogen atoms and/or hydrogen atoms introduced over time by, for example, valve control.

The substrate temperature is preferably selected from 20 to 1500°C, more preferably 30 to 1200°C, and optimally 50 to 1100°C.

The supply amount of the raw material gas is determined as appropriate depending on the desired thin film portion and the desired film formation rate.

The discharge power is preferably 0.001 to 20 W/crn",
More preferably, it is selected from O, Ol to 15 W/crn'', optimally from 0605 to IOW/crn'.

The pressure in the deposition chamber is preferably 1O-4 to 1OTorr,
It is preferably selected from 10-2 to 5 Torr.

The thin film of the heating resistor of the present invention obtained using the above-described thin film forming method has properties close to those of diamond. # For example, Vickers hardness 1800-5000, thermal conductivity 0
．． 3~2cal/cm*sec*"cj, resistivity 10"
It has properties of 3 to IQOΩsen, and since it contains germanium atoms, halogen atoms, and hydrogen atoms, it has extremely excellent flexibility.

Of course, a layer having appropriate protection and other functions may be provided on the monofunctional thin film W144 of the resistor of the present invention.

In the above description, the base body 2 is assumed to be a single body, but the base body 2 in the present invention may be a composite body. FIG. That is, the base body 2 is composed of a composite body of a base part 2a and a surface layer 2b, and for the base part 2a, for example, the base material explained in connection with FIG. 1 above can be used, and the surface layer 2b
For the surface layer 2b, a material with better adhesion to the functional thin film 4 formed thereon can be used.For example, the surface layer 2b can be made of an amorphous material having carbon atoms as a matrix or a conventionally known oxidized material. The device-like surface layer 2b made of materials or the like can be obtained by depositing appropriate raw materials on the base 2a by a method similar to the thin film forming method described above. Further, the surface layer 2b may be a normal glassy glaze layer.

Next, the outline of the manufacturing method of the heating resistor of the present invention will be explained.

FIG. 9 is a diagram showing an example of an apparatus used when forming a Ja thin film on the surface of a substrate. 1101 is a deposition chamber, 1102 to 1106 are gas cylinders, 110
7 to 1111 are mass flow controllers, and 111
2 to 1116 are inflow valves, 1117 to 1121
is an outflow valve, 1122-1126 is a gas cylinder valve, 1127-1131 is an outlet pressure gauge, 1132 is an auxiliary valve, 1133 is a lever, 1134 is a main valve, and 1135 is a leak valve. , 1136 has 1 vacuum gauge, 1137
is a base material of the resistor to be manufactured, 1138 is a heater, 1139 is a base support, and 1140 is a high voltage power supply.

1141 is an electrode, and 1142 is a shutter. In addition, 1142-1 is the electrode 1 when performing the sputtering method.
This is a target attached to 141.

For example, 1102 is sealed with CF4 gas (99.9% purity or higher) diluted with Ar gas, and 1103
GeH4 gas diluted with Ar gas (purity 99.9)
% or more) is sealed, and 1104 is 02 F diluted with Ar gas.

Gas (purity 99.9% or higher) is sealed.

Before the gas in these cylinders flows into the deposition chamber 1101, the valves 11 of each gas cylinder 1102 to 1106
22-112B and leak valve 1135 are closed, and inlet valves 1112-1118.
, outflow valves 1117-1121 and auxiliary valve 113
Make sure that valve 2 is open, then open main valve 1 first.
134 is opened to exhaust the inside of the deposition chamber 1101 and gas piping.

Next, the reading on the vacuum gauge 1136 is approximately 1.5X10-OTor.
When the temperature reaches r, the auxiliary valve 1132 and the inflow valve 1 are closed.
112-1116 and outflow valves 1117-1121 are closed. Thereafter, a valve of a gas pipe connected to a cylinder of gas to be introduced into the deposition chamber 1101 is opened to introduce a desired gas into the deposition chamber 1101.

Next, an example of a procedure for manufacturing a resistor of the present invention by a glow discharge method using one or more devices will be described.

Open the valve 1122 to remove CF4 from the gas cylinder 1102.
/Ar gas to flow out, open the valve 1123 to flow out the GeH4/Ar gas from the gas cylinder 1103, and set the outlet pressure gauge 1127.112817) pressure to 1 kg/cr.
Adjust to n'.

Next, gradually open the inlet valves 1112 and 1113 to allow the gas to flow into the mass flow controllers 1107 and 1108. Next, gradually open the outlet valves 1117 and 1118 and the auxiliary valve 1132 to allow the CF4/Ar gas and GeH
4/Ar gas is introduced into the deposition chamber 1101. At this time, the mass flow controllers 1107 and 1108 are adjusted so that the ratio between the flow rate of CF4/Ar gas and the flow rate of G e H4/Ar gas becomes a desired value, and the deposition chamber 110
Adjust the opening degree of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the main valve 1134 reaches the desired value. Then, the temperature of the base 1137 supported by the support 1139 in the deposition chamber 110.1 is heated by the heater 1138 to a desired temperature, and then the shutter 1142 is heated.
is opened to generate glow discharge within the deposition chamber 1101.

Then, by changing the opening degree of the outflow valves 1117 and 1118 manually or by an external drive motor, the flow rate of CF+/Ar gas and/or GeH+/A is changed.
The flow rate of r gas is changed over time according to a predesigned rate of change curve, thereby changing the content of Ge atoms, F atoms, or H atoms in IItI4 in the film thickness direction.

Next, an example of a procedure for manufacturing a resistor of the present invention by a sputtering method using the above-described apparatus will be described. Electrode 1 to which high voltage is applied by high voltage power supply 1140
High-purity graphite 1142-1 is placed as a target on 141 in advance, and in the same manner as in the glow discharge method, CF4/Ar gas from gas cylinder 1102 and GeH4/Ar gas from gas cylinder 1103 are supplied at desired flow rates. and introduce it into the composting chamber 1101.

The target 1142-1 is sputtered by opening the shutter 1142 and turning on the high voltage power supply 1140. At this time, the substrate 1137 is heated to a desired temperature by the heater 1138, and the pressure inside the deposition chamber 1101 is set to a desired pressure by adjusting the opening degree of the main valve 1134, as in the case of the glow discharge method. Then, as in the case of the glow discharge method described above, the outflow valve 1117.11
18 is performed to change the flow rate of CF4/Ar gas and/or the flow rate of G e H4/Ar gas over time according to a pre-designed rate of change curve. Ge atom, F
The content of atoms and/or HM molecules is changed in the film thickness direction.

Specific examples of the heating resistor of the present invention are shown below.

Example 1: An alumina ceramic plate was used as a substrate, and a heating resistance layer, which was a functional thin film, was formed on the surface of the substrate. The heating resistance layer was deposited by a glow discharge method using the apparatus shown in FIG. It was done. As raw material gas cF4/A r =
0, 5 (capacity ratio) and GeH4/Ar gas, 1
(capacity ratio) was used. The conditions during the deposition were as shown in Table 1. During the deposition, the opening degree of the valve was continuously changed to change the flow rate of the GeH4/Ar gas to form a heat generating resistor layer having the thickness shown in Table 1.

After forming an A1 layer on the formed resistance layer by electron beam evaporation, the A1 layer is formed by photolithography.
The layer was etched into the desired shape to form multiple pairs of electrodes.

Subsequently, predetermined portions of the resistive layer were removed by photolithography using an HF-based etching solution. Sho 1
In this example, the size of the resistance layer between the electrode pairs is 100 #Lm x 100 ILm. In this example, the heat generating elements formed between the electrode pairs are arranged at a pitch of 8 pieces/mm. A plurality of heat-generating resistor elements were fabricated on the same substrate so that the heat-generating resistance elements could be fabricated on the same substrate. In FIG. 10 which shows a partial cross-sectional view of the heating resistor element thus produced, 2 is a base, 4 is a heating resistor layer, and 6 and 7 are a pair of electrodes.

The electrical resistance of each heating resistor element thus obtained was measured and found to be 85Ω.

Furthermore, an electrical pulse signal was input to the heating resistor element obtained in this example to measure the durability of the heating resistor element. In addition, the duty of the electrical pulse signal is 50%,
Applied voltage 20V, drive frequency 0.5kl (!, 1.0k
Hz and 2.0kHz.

As a result, in all cases of driving at different driving frequencies, even when the electrical pulse signal input reached 1xIQIO times, the heating resistor element was not destroyed, and its resistance value hardly changed.

Example 2: The raw material gas was C2F6/ArxO,5 (capacity ratio) and G
A heating resistor layer having the same thickness was deposited in the same manner as in Example 1 except that the eH4/Ar gas was used as 1 (capacity ratio).

Next, when a heating resistor element was prepared in the same manner as in Example 1 and an electrical pulse signal was input, the heating resistor element was not destroyed even when the electrical pulse signal input reached 1×10 10 times. Further, no change in resistance value was observed.

Example 3: A heat generating resistor layer was deposited in the same manner as in Example 1, except that the G e H4/Ar gas flow rate was kept constant and the discharge power was continuously varied, to produce a heat generating resistor element.

When the heating resistor element thus obtained was driven in the same manner as in Example 1, it was confirmed that it had sufficient durability as in Example 1.

Example 4: A heat generating resistor layer was deposited in the same manner as in Example 2, except that the G e I (4/ Ar gas flow rate was kept constant and the discharge power was continuously varied) to produce a heat generating resistor element.

When the heating resistor element thus obtained was driven in the same manner as in Example 2, it was confirmed that it had sufficient durability as in Example 2.

[Effects of the Invention] According to the present invention as described above, thermal response is improved by using an amorphous material made of carbon atoms as a matrix and containing germanium atoms, halogen atoms, and hydrogen atoms as a monofunctional thin film. A heating resistor having extremely good properties, thermal conductivity, heat resistance and/or durability, and further flexibility is provided.

Furthermore, according to the present invention, the content of germanium atoms, halogen atoms, and/or hydrogen atoms in the functional thin film is unevenly distributed in the film thickness direction, which improves heat storage and heat dissipation properties, and the relationship between the substrate and the functional thin film. Various properties such as adhesion can be easily achieved.

[Brief explanation of the drawing]

1 and 8 are partial cross-sectional views of the heating resistor of the present invention. 2 to 7 are graphs showing the distribution of the content of germanium atoms, halogen atoms, and/or hydrogen atoms in the functional thin film. FIG. 9 is a diagram showing an apparatus used for manufacturing the heating resistor of the present invention. FIG. 10 is a partial cross-sectional view of a heating resistor element manufactured in an example of the present invention. 2: Substrate 4: Functional thin film 6.7: Electrode 1101: Deposition chamber 1137: Substrate Agent Patent attorney Tsumi Taira Yamashita Figure 1 Figure 8 Figure 70 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7

Claims (7)

[Claims] (1) A functional thin film made of an amorphous material having carbon atoms as a matrix and containing germanium atoms, halogen atoms, and hydrogen atoms is formed on the substrate, and in the functional thin film, germanium atoms, halogen atoms, and A heating resistor characterized in that/or hydrogen atoms are unevenly distributed in the film thickness direction. (2) The content of germanium atoms in the functional thin film is 0
．． The heating resistor according to claim 1, wherein the heating resistor has a content of 0,001 to 40 atom %. (3) The content of halogen atoms in the functional thin film is 0.0
The heating resistor according to claim 1, wherein the heating resistor has a content of 0.001 to 30 atom %. (4) Hydrogen atom content in the functional thin film is 0.000
The heating resistor according to claim 1, wherein the heating resistor has a content of 1 to 30 atom %. (5) The sum of the germanium atom content, halogen atom content, and hydrogen atom content in the functional thin film is 0.0
The heating resistor according to claim 1, wherein the heating resistor has a content of 0.001 to 40 atomic %. (6) The heating resistor according to claim 1, wherein the halogen atom is F or Cl. (7) The heating resistor according to claim 1, wherein the base has a surface layer made of an amorphous material containing carbon atoms as a matrix on the side on which the functional thin film is formed.