JPS61218101A - 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 [Field of Industrial Application] The present invention relates to a heating resistor, and particularly to a thin S heating resistor formed by forming a resistive thin film as a functional element on the surface of a base.

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

[Prior Art] Conventionally, heating resistors used as relatively small electric-to-thermal energy conversion elements in electronic or electrical equipment include thin II type, thick film type, and semiconductor type. There is. 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 heating resistor, the above-mentioned performance is not necessarily satisfactory, and further improvement of the characteristics is desired.

[Objective of the Invention 1 In view of the above-mentioned prior art, one of the objects of the present invention is to
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 618 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 silicon 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 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 H4 is made of an amorphous material having carbon atoms as a matrix and containing silicon atoms, halogen atoms, and hydrogen atoms. Halogen atoms include F, Cl,
Br, Cl, etc. can be used, and these may be used alone or in combination. As the halogen atom, F and Cl are particularly preferable, and F is particularly preferable.

The content of silicon 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 o or oo.

1 to 40 atom%, more preferably 0.0005 to 40 atom%
The content is 20 atomic %, preferably 0.001 to 10 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 atom%, more preferably 0.0005 to 30 atom%
The content is 20 atomic %, preferably 0.001 to 10 atomic %.

The hydrogen atom content in the mechanical thin film 4 is appropriately selected to obtain desired characteristics depending on the purpose of use of the resistor, but is preferably 0.0001 to 30 atomic %, and more preferably 0.0001 to 30 atomic %. The content is from .0005 to 20 atom %, preferably from 0.001 to 10 atom %.

The sum of the silicon 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, oo.

l~40 at%, more preferably 0.0005~
It is 30 atom %, preferably o, ooi to 20 atom %.

In the heating resistor of the present invention, an amorphous material (hereinafter referred to as ra-C:Si: (X)) made of carbon as a matrix and containing silicon atoms, halogen atoms, and hydrogen atoms.

H) May be abbreviated as J. Here, X represents a halogen atom) The tsuki1@thin g4 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:Si:(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 carbon atoms (
C) and silicon atoms (
A raw material gas for Si supply that can supply St), a raw material gas for X supply that can supply halogen atoms (X), and a hydrogen atom (
H) is introduced into the deposition chamber, and a glow discharge is generated in the deposition chamber using high frequency waves or microwaves to form a-C:Si:(X, H
) may be formed.

In addition, a-C:St:(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 A source gas for Si supply, a source gas for X supply, and a source gas for H supply may be introduced into the room.

In the above method, as the raw material gas for C supply, the raw material gas for Si supply, the raw material gas for X supply, and the raw material gas for H supply, in addition to gaseous materials 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 include methane (CH4), ethane (C2Ha), propane (C3Ha), n-butane (n-C4H1o), and penta7 (C5H12).
, ethylene (C2H4) as an ethylene hydrocarbon
, propylene CC3He), butene-1 (C+Ha)
, butene2 (C4Ha), inbutylene (C4
Examples of acetylene hydrocarbons include acetylene (C2H2), methylacetylene (CaH4), and butyne (C4H6), and examples of aromatic hydrocarbons include benzene (C6I(e)).

As raw materials for Si supply, for example, SiH4, Si2
Silicon hydride (silanes) such as H6,5i3Ha, 5i4Hxo, SiF4, (SiF2)5, (S i F
2) e, (S i F2) 4, Siz
F6, Si3FB, SiHF3, SiH2F2
．． 5fC14 (SiCl2)5. SiBr4, (SiB
r2) Silicon halides (silane derivatives substituted with halogen atoms) such as s, 5i2C16, 5i2C13F3
can be given.

Examples of raw materials for supplying X include halogens, halides, interhalogen compounds, halogen-substituted hydrocarbon derivatives, etc. Specifically, the halogens include F2. C12, Br2
．． I2. Halides include HF, HC1, HBr,
Hl, Hlff intergen compounds include BrF, Cl
F, ClF3, BrF5, BrF3. IF3, I
F7, ICl, IBr, halogen-substituted hydrocarbon derivatives include CF4, CHF3, CH2F2, CH3F
, CC14, CHC13, CH2Clz ,, CH2O
1, CB F4, CHB F3, CH2B F2,
CH3B r, C14, CHF3, CH2I2, CH
Examples include 3I.

As a raw material for H supply, for example, hydrogen gas.

and hydrocarbons such as saturated hydrocarbons, ethylene hydrocarbons, acetylene hydrocarbons, and aromatic hydrocarbons, which are also the raw materials for supplying the above C.

These raw materials may be used alone or in combination.

In the above thin film forming method, in order to control the amount of silicon atoms, the amount of halogen atoms, and the amount of hydrogen atoms contained in the thin film 11 to be formed, and the characteristics of the thin film 11, it is necessary to
Supply amount of raw material gas, discharge power.

Set the pressure in the deposition chamber as appropriate.

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/crn', more preferably 0.01 to 15 W/crn'.

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

The pressure in the deposition chamber is preferably 10-4 to 10 Torr,
It is preferably selected from 10-2 to 5 Torr (7).

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
．． 3~2cat/cm*5eca"o, resistivity 10-3
It has a property of ~106 Ωsen, and contains silicon atoms, halogen atoms, and hydrogen atoms, so it can have extremely excellent mechanical strength.

Of course, a layer having appropriate protection and other functions may be provided on the functional thin film 4 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, which can use a material with better adhesion to the functional thin film 4, is made of, for example, an amorphous material having carbon atoms as a host, a conventionally known oxide, or the like. Such a surface layer 2b can be obtained by depositing an appropriate raw material on the base za 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. 3 is a diagram showing an example of an apparatus used when forming a functional thin film on the surface of a substrate. 1101 is a deposition chamber, 1102 to 1106 are gas cylinders 41.1107
~1111 is a mass flow controller, 1112
~1116 are inlet valves, 1117~1121 are outlet valves, 1122~1126 are gas cylinder valves, 1127~1131 are outlet pressure gauges, 1132 is an auxiliary valve, 1133 is a lever, 1134 is a main valve, 1135 is a leak valve, 1136 is a vacuum gauge, 1137 is a base material of the resistor to be manufactured, 1138 is a heater, 1139 is a base support, 1140 is a It 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
SiH4 gas (purity 99.9) diluted with Ar gas
% or more) is sealed, and 1104 contains C2F diluted with Ar gas.

Gas (99.9% purity or higher) is sealed and 110%
5 contains 5f2H6 gas (purity 99) diluted with Ar gas.
．． 9% or more) are sealed. Before the gas in these cylinders is allowed to flow into the deposition chamber 1101, it is confirmed that the valves 1122 to 1126 and the leak valve 1135 of each gas cylinder 1102 to 110B+7 are closed, and the inflow valves 1112 to 1116 and the outflow valve 11
After confirming that 17 to 1121 and the auxiliary valve 1132 are open, the main valve 1134 is first opened to exhaust the inside of the deposition chamber 1101 and gas piping.

Next, the reading of vacuum gauge 1136 is about 1.5X10-6 Tor.
When the temperature reaches r, the auxiliary valve 1132° inflow valve 1
112-1116 and outflow 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 and discharge CF4 from the gas pump 1102.
/Ar gas flows out, valve 1123 is opened to flow out SiH4/At gas from gas cylinder 1103, and outlet pressure gauge 1127.1128 (7) pressure is set to 1 kg/cm.
', then gradually open the inlet valves 1112.1113 to allow flow into the mass flow controllers 1107.1108, then the outlet valves 1117.11.
18. Gradually open the auxiliary valve 1132 to release CF</Ar
gas and SiH4/Ar gas are introduced into the deposition chamber 101. At this time, the flow rate of CF4/Ar gas and Si
Adjust the mass flow controllers 1107 and 1118 so that the ratio with the flow rate of H4/Ar gas reaches the desired value, and check the reading on the vacuum gauge 1136 so that the pressure in the deposition chamber ttot reaches the desired value. while adjusting the opening degree of the main valve 1134. Then, the support 1 in the deposition chamber 1101
After heating the base 1137 supported by the heater 1138 to a desired temperature,
The shutter 1142 is opened to generate glow discharge within the deposition chamber 1tot.

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
141 is preliminarily subjected to ffR1 using high-purity graphite 1142-1 as a target. Similarly to the glow discharge method, CF4/Ar gas from gas cylinder 1102 and S i H4/Ar gas from gas cylinder 1103 are applied as desired, respectively. is introduced into the deposition chamber 1101 at a flow rate of .

The target 142-1 is sputtered by opening the shutter 1142 and turning on the high voltage power supply 1140. At this time, the base 1137 is heated by the heater 138.
As in the case of the glow discharge method, the deposition chamber tioi is heated to a desired temperature and the pressure inside the deposition chamber tioi is set to a desired value by adjusting the opening degree of the main valve 1134.

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

Example 1: An alumina ceramic plate was used as a base, and a heat generating resistor layer, which was a functional S film, was formed on the surface of the base. It was done by law. cF4/Ar=0.
5 (volume ratio) and SiH4/Ar gas, 1 (volume ratio) were used. The conditions during the deposition were as shown in Table 1. During the deposition, the opening degree of each valve and other conditions were kept constant, and a heat generating 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, 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 100p, mm x 100AL. In this example, the heat generating elements formed between the electrode pairs are arranged at a pitch of 8/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. 4, 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 6.7 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 1×10 10 times, and its resistance value hardly changed.

Example 2: The raw material gas was C2Fe/Ar=0.5 (capacity ratio) and S
A heating resistor layer having the same thickness was deposited in the same manner as in Example 1 except that 12Ha/Ar=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.

Example 5: An alumina ceramic plate was used as the 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 sputtering using the apparatus shown in FIG. It was. Graphite with a purity of 99.9% or more was used as a sputtering target, and CF 4 /Ar''0,5 (capacity ratio) and SiH+/Ar=0.1 (capacity ratio) were used as raw material gases.

The conditions during the deposition were as shown in Table 1. Also, the gas pressure in the deposition chamber during sputtering was 4XlO-2Torr.
Met. During the deposition, the opening degree of each valve and other conditions were kept constant to form a heating resistor layer having the thickness shown in Table 1.

Using the resistance layer thus formed, a heating resistor element was produced in the same manner as in Example 1, and an electrical pulse signal was input to the heating resistor element in the same manner as in Example 1.
As with Example 1, it was confirmed that the durability was excellent.

[Effects of the Invention] According to the present invention as described above, thermal response is improved by using an amorphous material containing carbon atoms as a matrix and silicon atoms, halogen atoms, and hydrogen atoms as a functional thin film. A heat generating resistor having extremely good properties, thermal conductivity, heat resistance and/or durability as well as mechanical strength is provided.

[Brief explanation of drawings]

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. 2: Substrate 4: Functional thin film 6.7: Electrode 1101: Deposition chamber 1137: Substrate

Claims (7)

[Claims] (1) A heating resistor characterized in that a functional thin film made of an amorphous material having carbon atoms as a matrix and containing silicon atoms, halogen atoms, and hydrogen atoms is formed on a substrate. (2) The content of silicon 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 40 atomic %. (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 silicon atom content, halogen atom content, and 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 40 atom %. (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.