JPS61218102A - 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 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 1 Heat-generating 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
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.

The thin film heating resistor of the present invention is characterized in that a functional thin film made of an amorphous material made of carbon atoms as a matrix and containing germanium atoms, halogen atoms, and hydrogen atoms is formed on a substrate. .

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 5WJ4 formed on its surface, and is suitable for use under heat during the formation of the functional thin [4] and during use. It is preferable that the substrate 2 has good durability against the heat generated by the functional thin film 115I4, and it is preferable that the substrate 2 has a higher electrical resistance than the functional thin film 4 formed on the surface thereof. 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, C as halogen atoms
1, Br, ■, etc. can be used, and these may be used alone or in combination.

As the halogen atom, F and C1 are particularly preferable, and F is particularly preferable.

The self-reflection rate 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 content of halogen atoms in the atomic functional thin film 4 is preferably o, oot to 10 at. oo.

1 to 30 atom%, more preferably 0.0005 to 30 atom%
The content is 20 atomic %, preferably 0.001 to 10 atomic %.

The content of hydrogen 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 0.0001 to 30 at.%, more preferably 0.0001 to 30 at.%. 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 o.

OO1 to 40 at%, more preferably 06000
The content is 5 to 30 atomic %, preferably 0.001 to 20 atomic %.

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. The functional thin film 4 consisting of (herein, halogen atoms) is formed by, for example, 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,
In order to form a thin lI4 made of H), basically the substrate 2 is placed in a deposition chamber under reduced pressure, and a raw material gas for C supply and germanium atoms that can supply carbon atoms (C) into the deposition chamber are added. (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. , a glow discharge is generated in the deposition chamber using high frequency or microwave, and a-C:Ge:(
What is necessary is to form a layer consisting of X, H).

In addition, a-C:Ge:(X,
In order to form the thin film 4 consisting of H), basically the substrate 2
is placed in a deposition chamber under reduced pressure, and when sputtering a target composed of C in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, the deposition What is necessary is to introduce a raw material gas for Ge supply, a raw material gas for X supply, and a raw material gas for H supply into the room.

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 supplying C include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, and acetylene hydrocarbons having 2 to 4 carbon atoms.

Aromatic hydrocarbons, etc., specifically saturated hydrocarbons include methane (CH4), ethane (C2H6), propa7 (C
3HB), n-butane (n-C4H10), penta7
(C5H12), x Tyrenic hydrocarbons include ethylene (C2H4), propylene (C3He), butene-1 (C4Ha), butene-2 (04H8)
, inbutylene (C4H8), pentene (Cs Hzo
), acetylene (C2
H2), methylacetylene (C3)14), butyne (
C4H6), benzene (Co
Ha) etc.

Examples of raw materials for supplying Ge include GeH4, Ge2
H6, Ge3 Ha, Ges HIO.

Ges H12, Gee H14, Ge7H18, Ge
Germanium hydride such as BHlB, Ge7H18, and G
eF4, (GeFz)s, (GeF2)a, (GeF2
)4, Ge2 F6, Ge3 Fg, GeHF3
, GeB2 F2 , GeC14(GeC12)s'
, GeBr4, (GeBr2) s.

Examples include Ge2 C16, Ge2 C13F3, etc. 17)/'Germanium halogenide (/X hydrogen halogenide derivative substituted with a halogen atom).

Examples of raw materials for supplying X include l\halogen, halides, interhalogen compounds, halogen-substituted hydrocarbon derivatives, and specifically F2. C12,Br
2. I2. Halides include HF, HCl, HBr
, HI, interhalogen compounds include BrF, CIF, C
lF3, BrF5. BrF3. IF3. IF7. IC
I, IBr, CF as a halogen-substituted hydrocarbon derivative
4, CHF3, CH2F2, CH3F, CC14
, CHC13, CH2C12, CH3Cl, CBr4.
CHBr3, CH2Br2, CH3Br, CI4,
Examples include 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 thin film forming method described above, in order to control the amount of germanium atoms, the amount of halogen atoms, 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.

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 performance and the desired film formation rate.

The discharge power is preferably 0.001 to 20 W/cm'', more preferably 0.01 to 15 W/crn'.

Optimally, it is selected from 0.05 to IOW/cm'.

The pressure in the deposition chamber is preferably 10-4 to 10 Torr,
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. That is, for example, Vickers hardness 1800-5000, thermal conductivity 0
．． 3~2cal/cm*5ecs'o, resistivity 10-
It has a property of 3 to 10 6 Ω·Cm, and contains germanium atoms, halogen atoms, and hydrogen atoms, so that it has extremely excellent flexibility.

Of course, a layer having appropriate protection and other functions may be provided on the functional thin film 1I4 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. The configuration of such an embodiment is shown in FIG. show,
That is, the base 2 is composed of a composite body of a base 2a and a surface layer 2b, and the base 2a can be made of the base material described above with reference to FIG. 1, and the surface layer 2b can be formed on the base material. The surface layer 2b, in which a material with better adhesion to the functional thin layer 114 can be used, is made of, for example, an amorphous material having carbon atoms as a matrix, a conventionally known oxide, or the like. Such a surface layer 2b
can be obtained by depositing appropriate raw materials on the base 2a by a method similar to the thin film forming method described above. Also,
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. 3 is a diagram showing an example of an apparatus used when forming a thin film on a substrate surface. 1101 is a deposition chamber, 1102 to 1106 are gas cylinders, j>'J, 110
7 to 1111 are mass flow controllers, and 111
2 to 1116 are inflow valves, 1117 to 1121
are outflow valves, 1122-1128 are gas cylinder valves, 1127-1131 are outlet pressure gauges, 1132 is an auxiliary valve, 1133 is a lever, 1134 is a main valve, and 1135 is a leak valve , 1136 is a vacuum gauge, and 1137
is the base material of the resistor to be manufactured, 1138 is the heater, 1139 is the base support, 1140 is the high voltage power supply, 1141 is the electrode, and 1142 is the shutter.6.1 1142- 1 is a target attached to the electrode 1141 when performing the sputtering method.

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 contains C2F 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
22-1126 and leak valve 1135 are closed, and inlet valves 1112-1116
, 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 vacuum gauge 1136 reads approximately 1.5XlO-6Tor.
When the temperature reaches r, the auxiliary valve 1132° inflow valve 1
112-ttte and outlet valves 1117-1121 are closed. Thereafter, a desired gas is introduced into the deposition chamber 1101 by opening the valve of the gas pipe connected to the cylinder of the gas to be introduced into the deposition chamber 11O1.

Next, an example of a procedure for manufacturing a resistor of the present invention by a glow discharge method using the above-described apparatus will be described.

Open the valve 1122 to remove CF4 from the gas cylinder 1102.
/Ar gas was allowed to flow out, valve 1123 was opened to allow GeH4/Ar gas to flow out from gas cylinder 1103, and the pressure of outlet pressure gauges 1127 and 1128 was adjusted to 1 kg/cm'.

Next, gradually open the inflow valves 1112 and 1113 to allow the flow into the mass flow controllers 1107 and 1108. Next, gradually open the outflow valves 1117 and 1118 and the auxiliary valve 1132 to allow the CF4/At gas and G1 to flow.
3H4/Ar gas is introduced into the deposition chamber 1101. At this time, the flow rate of CF4/Ar gas and G e H4/
Adjust the mass flow controllers 1107 and 1118 so that the ratio with the flow rate of AT gas becomes the desired value, and adjust the vacuum gauge 11 so that the pressure in the deposition chamber 1toi becomes the desired value.
Adjust the opening degree of the main valve 1134 while checking the reading of 36. Then, the temperature of the base 1137 supported by the support 1139 in the deposition chamber 1101 is heated by the heater 1138 to a desired temperature, and then the shutter 1142 is opened to generate a glow discharge in the deposition chamber 1101. .

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/At gas is supplied from gas cylinder 1102 and GeH4/Ar gas is supplied from gas cylinder 1103 at desired flow rates. and introduced into the deposition chamber 1101.

By opening the shutter 1142 and turning on the high voltage power supply 1140, the target/metal 1142-1 is sputtered. At this time, the base 1137 is heated by the heater 1138.
As in the case of the glow discharge method, the deposition chamber 1101 is heated to a desired temperature and the pressure inside the deposition chamber 1101 is set to a desired value by adjusting the opening degree of the main valve 1134.

A specific example of the heating resistor of the present invention will be 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. CF4 /ar=o as raw material gas
, 5 (capacity ratio) and Ge1(+/Ar=0.1 (
(capacity ratio) was used. The conditions during the deposition were as shown in Table 1. Incidentally, during the deposition, the opening degree of each valve and other conditions were kept constant, and a heating resistor layer having the thickness shown in Table 1 was formed.

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, the resistive layer at the octopus leg portion was removed using an HF-based etching solution using photolithography technology. In this example, the size of the resistance layer between the electrode pairs is 100 pm x 10,100 p. In this example, the heat generating elements formed between the electrode pairs have a pitch of 8 pieces/
A plurality of heat generating resistive elements were fabricated on the same substrate so as to be arranged in mm. In Fig. 4, which shows a partial cross-sectional view of the heating resistor element thus produced, 2 is a base;
4 is a heating resistance layer, and 6.7 is a pair of electrodes.

The electrical resistance of each heating resistor element thus obtained was measured and found to be 80Ω.

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 0.5kHz, 1. okH
z, 2.0kHz.

As a result, in all cases of driving at different driving frequencies, the heating resistor element was not destroyed even when the electrical pulse signal input reached 1010 times, and its resistance value hardly changed.

Example 2: The raw material gas was C2Fe/Ar=0.5 (volume ratio) and G
A heating resistor layer having the same thickness was deposited in the same manner as in Example 1 except that eH4/A r = 0, 1 (capacitance 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 1010 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 substrate was changed to #7059 glass manufactured by Corning Incorporated 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 substrate was changed to #7059 glass manufactured by Corning Incorporated 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, by using an amorphous material containing carbon atoms as a matrix and containing +J rumanium atoms, halogen atoms, and hydrogen atoms as a functional thin film, A heating resistor is provided which has extremely good thermal responsiveness, thermal conductivity, heat resistance and/or durability, and furthermore, excellent flexibility.

[Brief explanation of the drawing]

1 and 2 are partial cross-sectional views of the heating resistor of the present invention. FIG. 3 is a diagram showing an apparatus used for manufacturing the heating resistor of the present invention. FIG. 4 is a partial cross-sectional view of a heating resistor element manufactured in an example of the present invention. 22 Substrate 4: Functional thin film 6.7: Electrode 1101: Deposition chamber 1137: Substrate Fig. 1 Fig. 2 Fig. 4

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,
heating resistor. (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 C1. (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.