JPS61218113A - 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 Application in Isl Industry] The present invention relates to a heat generating resistor, and more particularly to a filIII5i heat generating 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] Heating resistors conventionally used as relatively small electric-to-thermal energy conversion elements in electronic or electrical equipment include thin film type, thick S type, and semiconductor type. . Among them, thin S-type ones consume less power than other types and have relatively good thermal response, 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 ms 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 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 containing carbon atoms as a matrix and halogen atoms is formed on a substrate, and in the functional thin film, halogen atoms are arranged in the thickness direction. It is characterized by uneven distribution.

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 by the functional thin film 4, and the base 2 preferably has a higher electrical resistance than the functional thin film [4] formed on the surface thereof. In this case, depending on the purpose of use of the resistor, a substrate 2 having low thermal conductivity or a substrate having high thermal conductivity can be used.

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 monofunctional thin film 4 is made of an amorphous material containing carbon atoms as a host and halogen atoms. Halogen atoms include F%Cl, Br.

(3) 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 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 atomic %, preferably o, ooi to 10 atomic %.

An advantage of the present invention is that the distribution of halogen atoms in the functional thin film 4 is non-uniform in the film thickness direction.

The change in the content of halogen atoms in the functional thin film 4 in the film thickness direction may be such that the content gradually increases from the base 2 side to the surface side, or may be such that the content decreases conversely. Furthermore, the change in the halogen atom content may have a maximum value or a minimum value in the thin film 4.
The change in the content of halogen atoms in the functional thin film 4 in the film thickness direction is appropriately selected so as to obtain desired characteristics depending on the use of the heating resistor.

2 to 7 show specific examples of changes in the content of halogen atoms in the film thickness direction in the functional thin film 4 of the heating resistor of the present invention. In these figures, the vertical axis represents the interface with the base 2. represents the distance T in the film thickness direction from
The horizontal axis represents the halogen atom content C. In each figure, the scales of the vertical axis T and horizontal axis C are not necessarily uniform, and the scales are adjusted to bring out the characteristics of each figure. It is being forced to change. Therefore, in actual application, various distributions are used for each diagram based on the differences in specific numerical values.

In the heating resistor of the present invention, an amorphous material made of carbon as a matrix and containing a halogen atom (hereinafter sometimes abbreviated as "a-C:XJ", or a halogen atom),
) is the functional thin M4.

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, to form a thin film 4 made of a-C:X by a glow discharge method, the base 2 is basically placed in a deposition chamber under reduced pressure, and carbon atoms (C) can be supplied into the deposition chamber. A raw material gas for C supply and a raw material gas for X supply that can supply halogen atoms (x) are introduced, and at this time, high frequency or microwave radiation is applied in the deposition chamber while changing the amount of the raw material gas introduced for X supply. It is only necessary to generate a glow discharge using the above to form a calendar consisting of a-C:X on the surface of the substrate 2.

Furthermore, in order to form the thin film 4 made of a-C:X by sputtering, the substrate 2 is basically placed in a deposition chamber under reduced pressure, and an inert gas such as Ar or He is used in the deposition chamber. Alternatively, when sputtering a target made of C in an atmosphere of a mixed gas based on these gases, a source gas for supplying X may be introduced into the chamber Ihj, and the amount introduced may be varied at this time.

In the above method, as the raw material gas for C supply and the raw material gas for X supply, in addition to those in a gaseous state at room temperature and normal pressure, substances that can be gasified under reduced pressure 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 (C2H6), propane (C3Ha), n-butane (n-C4HIO), pentane (C5H12),
Ethylene hydrocarbons include ethylene (C21(4)
, propylene (C3Ha), butene-1 (C4H8
), butene-2 (C4H8), inbutylene (C
4H8), pentene (C5HIO), '7 Cetylenic hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (C4Ha), and aromatic hydrocarbons include benzene (C8Hs).

As a raw material for supplying X, for example, halogen.

Halides, interhalogen compounds, halogen-substituted hydrocarbon derivatives, etc. Specifically, halogens include F2, C:
I2, Br2.12, HF as halide
, HCl, HBr, HI, E as an interhalogen compound
rF, ClF, ClF3, BrF5, BrF3. I
F3, IF7, ICl, more r, halogen-substituted hydrocarbon derivatives include CF4, CHF3, Cl (2F
2, CH3F, CCl4. CHCl3, CH2C1
2, CH2O1, CBr4, CHBr3, CH2B
r2, CH3Br, Cl4, CHI3, CH2I2
, CH3I, etc.

These raw materials may be used alone or in combination.

In the above thin film forming method, in order to control the amount of halogen 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, the supply amount of source gas, the discharge power, the pressure in the deposition chamber, etc. etc., as appropriate.

In particular, in order to obtain the functional thin film 4 of the present invention in which the distribution of halogen atoms is non-uniform in the film thickness direction, it is preferable to change the amount of halogen atoms introduced into the deposition chamber over time, for example, by controlling a valve.

The substrate temperature is preferably selected from 20 to 1500°C, more preferably 3ON1200°C, and optimally 50 to 1100°C.

The supply amount of raw material gas depends on the desired N film performance and the target f.
ItII! Laws are applied as appropriate depending on the speed.

The discharge power is preferably 0.001 to 20 W/crn',
More preferably, it is selected from 0,01-15W/crn', optimally from 0.05 to IOW/crn'.

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
, 3~2 c a l / cm m5ect d
eg, has a resistivity of 10-3 to 106Ωcm,
Furthermore, since it contains a halogen atom, it can be obtained with extremely excellent chemical stability and thermal stability.

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 of a material formed thereon. The surface layer 2b can be made of, for example, an amorphous material having carbon atoms as a matrix or a conventionally known oxide. . Such a surface layer 2b can be obtained by depositing an appropriate raw material on the base 2a by a method similar to the thin film forming method described above. Further, the first surface layer 2b may be a normal glassy glaze layer.

Next, an outline of a method for manufacturing a heating resistor according to the present invention will be explained.

FIG. 9 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, and 1107 to 1106 are gas cylinders;
1lll is a mask row controller, and 1112~
1116 is an inflow valve, 1117-1121 is an outflow valve, 1122-112B is a gas cylinder valve, 1127-1131 is an outlet pressure gauge, 1132 is an auxiliary valve, 1133 is a lever, 1134 is the main valve, 1135 is the leak valve, 113B is the vacuum gauge, 1137 is the base material of the resistor to be manufactured, 1138 is the heater, 1139 is the base support, 1140 is the high temperature It is a 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
C2F6 gas (purity 99.9
% or more) are sealed. Before the gas in these cylinders flows into the deposition chamber 1101, each gas cylinder 11
Confirm that the valves 1122-1126 and leak valve 1135 of 02-1106 are closed, and also that the inlet valve 1112-1tis and the outlet valve 1117-1
121 and the auxiliary valve 1132 are opened, first open the main valve 1134 to close the deposition chamber 11.
When the reading on the vacuum gauge 1136 reaches approximately 1.5×10 −6 Torr, the auxiliary valve 1132, inlet valves 1112 to 1116, and outlet valves 1117 to 1121 are closed. After that, the valve of the gas pipe connected to the cylinder of the gas to be introduced into the deposition chamber 1101 is opened to introduce the desired gas into the deposition chamber 1101.
Introduced within 1.

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 the CF from the gas cylinder t102.
4/Let the Ar gas flow out, adjust the pressure of the outlet pressure gauge 1127 to 1 kg/am'', and then gradually open the inflow valve 1112 to allow it to flow into the mass flow controller 1107.Subsequently, the outflow valve 1117. Gradually open the auxiliary pulp 1132 to introduce CF4/Ar gas into the deposition chamber l.
Introduce into lot. At this time, the mass flow controller 1107 controls the flow rate of CF4/Ar gas to the desired value.
while checking the reading on the vacuum gauge 1136 so that the pressure inside the deposition chamber 1101 reaches the desired value.
Adjust the opening degree of 134. Then, the temperature of the base 1137 supported by the support 1139 in the deposition chamber ttot 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. . Then, the flow rate of the CF4/At gas is changed over time according to a pre-designed rate of change curve by operating the opening degree of the outflow valve 1117 manually or by using an externally driven motor, etc. The content of F atoms is changed 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 CF4/Ar gas is introduced into deposition chamber 1101 from gas cylinder 1102 at a desired flow rate in the same manner as in the glow discharge method. 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, in the same way as in the case of the glow discharge method, the opening degree of the outflow valve 1117 is changed to change the flow rate of the CF4/Ar gas over time according to a pre-designed rate of change curve. The content of F atoms in the film 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. CF4/Ar gas, 5 (capacity ratio), was used as the raw material gas. The conditions during the deposition were as shown in Table 1. Incidentally, during the deposition, the opening degree of the valve was continuously changed to change the flow rate of the CF4/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, a predetermined portion of the resistive layer was removed using a photolithography technique using an HF-based etching solution. still,
In this example, the size of the resistance layer between the electrode pairs is 100 ILm x 100 JLm. 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. FIG. 1O shows a partial cross-sectional view of the heat-generating resistor element thus produced, in which 2 is a base, 4 is a heat-generating 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 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 0.5kHz, 1.0kHz
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: Source gas was C2F8/Ar=0, 2 (capacity ratio),
A heating resistor layer having the same thickness was deposited in the same manner as in Example 1 except that the discharge power was 2 W/crn'.

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: Changing the substrate to Corning #7059 glass, CF
A heat generating resistor layer was deposited in the same manner as in Example 1 except that the 4/Ar gas flow rate was changed 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: Changing the substrate to Corning #7059 glass, C2
A heat generating resistor layer was deposited in the same manner as in Example 2 except that the Fe/Ar gas flow rate was changed 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 was formed as a functional thin film 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 CF4/Ar gas, 5 (capacity ratio), was used as a raw material gas. The conditions during the deposition were as shown in Table 1. Further, the gas pressure in the deposition chamber during sputtering was 4×10 −2 Torr. Incidentally, during the deposition, the opening degree of the valve was continuously changed to change the flow rate of the CF4/Ar gas to form a heat generating 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, by using an amorphous material made of carbon atoms as a matrix and containing halogen atoms as a functional thin film, thermal responsiveness, thermal conductivity, and heat resistance are improved. sex and/or
Alternatively, a heating resistor having extremely good durability, chemical stability, and thermal stability is provided.

Furthermore, according to the present invention, the content of halogen atoms in the functional thin film is distributed unevenly in the film thickness direction.
Various properties such as heat storage, heat dissipation, and adhesion between the substrate and the functional thin film 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 halogen atom content 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 Seki Yamashita Child 1 Figure 8 Figure 1 o Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 OC

Claims (4)

[Claims] (1) A functional thin film made of an amorphous material containing carbon atoms as a matrix and halogen atoms is formed on a substrate, and the halogen atoms are unevenly distributed in the film thickness direction in the functional thin film. A heating resistor characterized by: (2) 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 %. (3) The heating resistor according to claim 1, wherein the halogen atom is F or Cl. (4) The heat generating 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.