JP2003347101A - Resistor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resistor in which a heating layer having a small resistance value and stress is stably formed at a high film deposition rate. <P>SOLUTION: This resistor comprises a heating layer 3 composed of polysilicon formed on a substrate 1 by a catalyst CVD method. A catalyst body used in the catalyst CVD method is comprised of a catalytic element selected from Ta, W and Mo, and the heating layer 3 contains the catalytic element of 0.5 ppm-10% by atom and a group V element of 1.0 ppm-0.3% by atom in the periodic table. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistor having a polysilicon layer formed thereon.

[0002]

2. Description of the Related Art Conventionally, when a heating layer of a resistor is formed by a thin film forming method, a vacuum evaporation method, a plasma CVD method,
An optical CVD method, a thermal CVD method, a reactive sputtering method, an ion plating method, or the like is used.

For example, when the heat generating layer is formed of an amorphous silicon layer, a film is formed on the amorphous silicon layer by a plasma CVD method.

According to Japanese Patent Application Laid-Open No. 9-120907,
A technique has been reported in which a resistor made of Ta, Si, C, and O is manufactured by high-frequency sputtering.

In Japanese Patent Application Laid-Open No. 11-10879, a heating resistor in which a metal is added to C and SiO by a plasma CVD method or the like is reported.

[0006]

[SUMMARY OF THE INVENTION However, when forming the resistor by a plasma CVD method, a sputtering method, or the like as described above, the low resistance membrane, particularly resistivity 10 ³ ~10 ⁰ (Ω · cm In order to form the film (1), it is necessary to dope a large amount of boron, phosphorus, or the like, which results in a low film formation rate, an increase in production cost, and is not suitable for mass production.

In addition, with such a heat generating layer, the film stress is increased, thereby reducing the adhesion, and as a result, a large number of defects such as peeling have occurred.

In view of the above circumstances, the inventor of the present invention has made intensive studies and found that the catalyst body was further converted to T using a catalytic CVD method.
This problem is solved by using a catalyst element selected from a, W, and Mo, and by including a Group V element of the periodic table at an atomic ratio of 1.0 ppm to 0.3%. I found that.

Accordingly, the present invention has been completed based on the above findings, and an object of the present invention is to provide a resistor in which a low-resistance, low-stress polysilicon layer is stably formed at a high film forming rate.

[0010]

A resistor according to the present invention is a resistor in which a polysilicon layer is formed on a substrate by a catalytic CVD method.
a, W, and Mo. The polysilicon layer contains a catalyst element at an atomic ratio of 0.5 ppm to 10% and a group V element of the periodic table in an amount of 1.0 ppm to 1.0 ppm.
It is characterized by containing at an atomic ratio of 0.3%.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A resistor according to the present invention will be described below with reference to the drawings, taking an ink-jet heating section as an example.

FIG. 1 is a sectional view of a main part of an ink-jet heating section which is a resistor according to the present invention. FIG. 2 is a diagram showing a schematic configuration of the catalytic CVD method according to the present invention.

According to the resistor shown in FIG. 1, an electrode 2 made of a metal such as aluminum or chromium is formed on an insulating substrate 1 such as glass or ceramics, which is the base,
The heating layer 3 as the polysilicon layer is formed on the electrode 2 by a catalytic CVD method, and another electrode 4 made of a metal such as aluminum or chromium is formed on the heating layer 3.

The electrodes 2 and 4 may be formed by a vacuum evaporation method or a sputtering method.

The heating layer 3 is made of polysilicon. As for polysilicon, carbon or nitrogen and oxygen may be further doped.

In the present invention, the group V element of the periodic table is adjusted to 1.0 ppm or more for adjusting the resistance value of the heat generating layer 3.
It is contained at an atomic ratio of 0.3%. The group V element of the periodic table includes phosphorus (P).
There are s, Sb, and Bi, and all elements are within the scope of the present invention.

The specific resistance of the heat generating layer 3 is controlled to 4.3 × 10 ^{3 to} 7.9 × 1 by the group V element of the periodic table.
It can be in the range of ⁰ Ω · cm.

The heat generating layer 3 is formed by a catalytic CVD method. For reference, the technique described in Japanese Patent Application Laid-Open No. 6-338391 may be used.

FIG. 2 shows the configuration of a catalytic CVD apparatus. As a preferred example, a case where phosphorus (P) is used as a Group V element of the periodic table will be described.

In FIG. 1, reference numeral 5 denotes a vacuum vessel, and a support 6 is disposed inside the vacuum vessel 5, and a substrate 7 for film formation is disposed on the support 6. Reference numeral 8 denotes a gas introduction unit, and the filament 9 as the catalyst is arranged between the gas introduction unit 8 and the substrate 7 for film formation.

When a semiconductor gas is introduced, the gas is ejected from a gas introduction section 8 and a film is formed on a film-forming substrate 7 through a filament 9.

The conditions for this film formation are, for example, a degree of vacuum of 1.33 P
a, The substrate temperature is 300 ° C., and the temperature of the catalyst (filament 9) is 2200 ° C.

As a raw material gas, a silicon hydride gas (monosilane, disilane) or the like is used, and as a carrier gas, a generally used hydrogen gas or an argon gas is used. Further, a small amount of doping gas may be added for adjusting the resistance value.
A gas such as H ₃ may be used.

According to the present invention, the catalyst body contains Ta, W,
The catalyst body is made of a catalyst element selected from Mo, and the catalyst body temperature is increased to, for example, 2200 ° C. to evaporate the catalyst body and incorporate the catalyst body element into the thin film layer.

Thus, according to the present invention, such a catalyst CV
Low doping gas (gas such as PH ₃ ) by D method
By simply adding, a film having a desired specific resistance could be obtained at low cost.

According to an experiment repeatedly performed by the present inventors,
When the catalyst element is not contained, the P content: 50
On the other hand, according to the present invention, if the P content is 1.0 ppm (0.5%),
Thus, a film having a specific resistance of 4.3 × 10 ³ Ω · cm or less was obtained.

Further, in the present invention, since the film is formed by the catalytic CVD method, the film is not damaged by plasma, whereby the internal stress of the film is reduced, and a film which is hard to peel off can be formed.

[0028]

EXAMPLE 1 As shown in FIG. 3, a substrate 11 (40 mm × 10 mm × 0.1 m thick) made of AF45 glass was used.
m) on the heat generating layer 13 by catalytic CVD (catalyst body: Ta)
Formed by This layer has a thickness of 2
A polysilicon layer was formed to a thickness of 000 mm.

According to the figure, an end of a substrate 11 is fixed to a substrate support 10 and a thin film layer (heating layer) 13 is formed on the substrate 11 to measure the amount of warpage δ. Then, the internal stress was measured.

A substrate 1 (40 mm × 10 mm) made of # 7059 glass was used for measuring the crystallization ratio and the resistance.
X thickness 1 mm) on the heat generating layer 3 by catalytic CVD (catalyst:
Ta) to be used for the heating resistor. This layer was formed as a polysilicon layer with a thickness of 20000 ° under the film forming conditions shown in Table 1. This sample was analyzed using a spectroscopic ellipsometer <Spectral ellipsometer M manufactured by SOPRA (France).
The crystallization ratio was measured using OSS Model ES4G>. As a result, the crystallization ratio was 62%, and a good polysilicon film was obtained. Further, a comb-shaped electrode was deposited on this sample, and the measurement was performed. As a result, the specific resistance was 3.0 × 10 ²
Ω · cm, and good results were obtained.

On the other hand, to measure other characteristics, use # 7
An aluminum electrode 2 having a width of 1 mm is deposited on a substrate 1 (40 mm × 10 mm × thickness 1 mm) made of 059 glass,
The heat generating layer 3 is formed thereon by a catalytic CVD method (catalyst: Ta) to be used for a heat generating resistor. This layer was formed as a polysilicon layer with a thickness of 20,000 ° under the film forming conditions shown in Table 1.

[0032]

[Table 1]

When the internal stress of the resistor of the present invention thus obtained was measured from the amount of warpage, there was no such warpage. Furthermore, an electrode having a width of 1 mm was vapor-deposited on the resistor in the cross direction, and the presence or absence of heat generation was evaluated.
Sufficient heat generation could be confirmed.

(Example 2) Next, when fabricating the resistor shown in (Example 1), a catalyst was used for forming the heating layer.
The resistance was changed in the range of 00 to 2500 ° C., and other film forming conditions were set in the same manner as the resistor of (Example 1), and various resistors were manufactured.

By increasing or decreasing the temperature of the catalyst in this way, various resistors were prepared in which the content of the catalyst element Ta was varied in various ways to 0.05 ppm or more. When the specific resistance, heat generation, internal stress, and adhesion of these resistors were measured, the results shown in Table 2 were obtained.

The evaluation of heat generation is classified into three types, ○, Δ, and ×, and the mark ○ indicates that the standard calorific value is satisfied, and the mark Δ indicates that only a part of the standard calorific value is satisfied. , X indicate the case where the entire surface does not satisfy the specified calorific value.

In addition, the evaluation of the adhesion was classified into three types of ○, Δ, and ×, and the mark ○ indicates that no film peeling was observed.
The mark “△” indicates a state in which film peeling occurs only partially, and the mark “×” indicates a state in which film peeling occurs over the entire surface.

[0038]

[Table 2]

As is clear from this table, it is found that the content of the catalyst element increases and the specific resistance decreases as the catalyst temperature increases. This is because the catalyst element evaporates and the element enters the film when the temperature of the catalyst increases. Then, as the catalyst element enters the film,
It can be seen that the specific resistance was reduced and the heat generation was improved.

In the case of Ta, the temperature of the catalyst is 2100 ° C. to 2 ° C.
At 300 ° C., good results were obtained in both heat generation and adhesion. At a catalyst body temperature of 2400 ° C., the catalyst element was excessively contained in the film, resulting in a rough film and peeling off. In addition, the temperature may be too high and the catalyst may be cut. Further, at a temperature of 2500 ° C. or higher, the catalyst body was always cut off during the film formation, resulting in that the film did not adhere.

Regarding the internal stress, a general plasma C
If it is an amorphous silicon film produced by the VD method,
The value is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ), but for the resistor manufactured in this example, it is a considerably small value (one order of magnitude smaller), Has a remarkable effect.

(Example 3) Next, in producing the resistor shown in (Example 1), in forming the thin film layer (heating layer 13), the flow rate of PH ₃ gas (diluted to 0.2% with hydrogen). Used gas: 40pp for conditions with low P content
is changed in the range of 0 to 300 sccm, and the SiH ₄ gas is set at a flow rate of 20 sccm, and other film forming conditions are set in the same manner as the resistor of (Example 1). Then, various resistors were manufactured.

That is, when forming a thin film layer,
By increasing or decreasing the PH ₃ gas flow rate to the SiH ₄ gas, to produce a variety of resistor content was changed in several as to the 0 to 1.2% of P (phosphorus).

When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 3 were obtained.

[0045]

[Table 3]

As is evident from the table, it can be seen that as the PH ₃ flow rate increases, the phosphorus element content increases and the specific resistance decreases. This is because, as the PH ₃ flow rate increases, the flow ratio with respect to the SiH ₄ gas increases, and a large amount of the phosphorus element enters the silicon film.
Then, it can be seen that the specific resistance was reduced and the heat generation was improved by the phosphorus element entering the film.

The phosphorus content is 1.0 ppm to 0.3 ppm.
%, Good results were obtained in both heat generation and adhesion.

When the phosphorus content is 0.8 ppm or less, the specific resistance increases and no heat is generated. On the other hand, when the phosphorus content is 0.52% or more, the phosphorus element is excessively contained in the film, and the internal stress increases. As a result, the warpage of the substrate increases, and the film peels off. As a result, the film became a film and peeled off.

(Example 4) In this example, as in (Example 2), the resistor shown in (Example 1) was produced in the case where W was used instead of the example in which the catalyst element was Ta.

According to this resistor, in forming the heat generating layer, the catalyst was changed in the range of 1500 to 3000 ° C., and other film forming conditions were set in the same manner as the resistor of (Example 1). A resistor was manufactured.

By increasing or decreasing the temperature of the catalyst in this way, various resistors were prepared in which the content of the catalyst element W was varied in various ways to 0.05 ppm or more. When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 4 were obtained.

[0052]

[Table 4]

As is clear from this table, it is understood that the content of the catalyst element increases and the specific resistance decreases as the catalyst temperature increases. This is because the catalyst element evaporates and the element enters the film when the temperature of the catalyst increases. Then, as the catalyst element enters the film,
The specific resistance is reduced, and the heat generation is improved.

In the case of W, the temperature of the catalyst is from 2000 ° C. to 25 ° C.
At 00 ° C., good results were obtained for both heat generation and adhesion. At a catalyst temperature of 2700 ° C., the catalyst element was excessively contained in the film, resulting in a rough film and peeling off. In addition, the temperature may be too high and the catalyst may be cut. Further, at a temperature of 3000 ° C. or more, the catalyst body was always cut off during the film formation, and the film did not adhere.

Regarding the internal stress, a general plasma C
If it is an amorphous silicon film produced by the VD method,
The value is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ), but for the resistor manufactured in this example, it is a considerably small value (one order of magnitude smaller), Has a remarkable effect.

(Example 5) Next, in producing the resistor shown in (Example 4), in forming the thin film layer (heating layer 13), the flow rate of PH ₃ gas (diluted to 0.2% with hydrogen) was used. Used gas: 40pp for conditions with low P content
is changed in the range of 0 to 300 sccm, and the SiH ₄ gas is set at a flow rate of 20 sccm, and other film forming conditions are set in the same manner as the resistor of (Example 1). Then, various resistors were manufactured.

That is, when forming a thin film layer,
By increasing or decreasing the PH ₃ gas flow rate to the SiH ₄ gas, to produce a variety of resistor content was changed in several as to the 0 to 1.05% of P (phosphorus).

When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 5 were obtained.

[0059]

[Table 5]

As is evident from the table, it can be seen that as the PH ₃ flow rate increases, the phosphorus element content increases and the specific resistance decreases. This is because, as the PH ₃ flow rate increases, the flow ratio with respect to the SiH ₄ gas increases, and a large amount of the phosphorus element enters the silicon film.
Then, it can be seen that the specific resistance was reduced and the heat generation was improved by the phosphorus element entering the film.

The phosphorus content is from 1.3 ppm to 0.2 ppm.
By containing at an atomic ratio of 7%, good results were obtained in both heat generation and adhesion.

When the phosphorus content is 0.9 ppm or less, the specific resistance increases and no heat is generated. On the other hand, if the phosphorus content is 0.42% or more, the phosphorus element is excessively contained in the film, and the internal stress increases. As a result, the warpage of the substrate increases, the film peels off, and the film becomes rough. As a result, the film became a film and peeled off.

(Example 6) In this example, as in (Example 2), the resistor shown in (Example 1) was produced by using Mo instead of the embodiment using Ta as the catalytic element.

According to this resistor, in forming the heat generating layer, the catalyst was changed in the range of 1500 to 3000 ° C., and other film forming conditions were set in the same manner as in the resistor of (Example 1). A resistor was manufactured.

By increasing or decreasing the temperature of the catalyst in this way, various resistors were prepared in which the content of the catalyst element Mo was changed to 0.04 ppm or more. When the specific resistance, heat generation, internal stress and adhesion of these resistors were measured, the results shown in Table 6 were obtained.

[0066]

[Table 6]

As is clear from this table, it is found that the content of the catalyst element increases and the specific resistance decreases as the catalyst temperature increases. This is because the catalyst element evaporates and the element enters the film when the temperature of the catalyst increases. Then, as the catalyst element enters the film,
The specific resistance is reduced, and the heat generation is improved.

In the case of Mo, the temperature of the catalyst body is from 2000 ° C. to 2 ° C.
At 700 ° C., good results were obtained for both heat generation and adhesion. At a catalyst body temperature of 2800 ° C., the catalyst element was too much contained in the film, resulting in a coarse film and peeling off. In addition, the temperature may be too high and the catalyst may be cut. Further, at a temperature of 3000 ° C. or more, the catalyst body was always cut off during the film formation, and the film did not adhere.

Regarding the internal stress, a general plasma C
If it is an amorphous silicon film produced by the VD method,
The value is 1.0 × 10 ^{8 to} 7.5 × 10 ⁸ (N / m ² ), but for the resistor manufactured in this example, it is a considerably small value (one order of magnitude smaller), Has a remarkable effect.

(Example 7) Next, in producing the resistor shown in (Example 6), in forming the thin film layer (heating layer 13), the flow rate of PH ₃ gas (diluted to 0.2% with hydrogen) was used. Used gas: 40pp for conditions with low P content
is changed in the range of 0 to 300 sccm, and the SiH ₄ gas is set at a flow rate of 20 sccm, and other film forming conditions are set in the same manner as the resistor of (Example 1). Then, various resistors were manufactured.

That is, when forming a thin film layer,
By increasing or decreasing the PH ₃ gas flow rate to the SiH ₄ gas, to produce a variety of resistor content was changed in several as to the 0 to 0.77% of P (phosphorus).

When the specific resistance, heat generation, internal stress, and adhesion of these resistors were measured, the results shown in Table 7 were obtained.

[0073]

[Table 7]

As is evident from the table, it can be seen that as the PH ₃ flow rate increases, the phosphorus element content increases and the specific resistance decreases. This is because, as the PH ₃ flow rate increases, the flow ratio with respect to the SiH ₄ gas increases, and a large amount of the phosphorus element enters the silicon film.
Then, it can be seen that the specific resistance was reduced and the heat generation was improved by the phosphorus element entering the film.

Further, the phosphorus content is from 1.2 ppm to 0.2 ppm.
By containing at an atomic ratio of 3%, good results were obtained in both heat generation and adhesion.

When the phosphorus content is 0.8 ppm or less, the specific resistance increases and no heat is generated. On the other hand, when the phosphorus content is 0.35% or more, the phosphorus element is excessively contained in the film, and the internal stress increases, whereby the warpage of the substrate increases, the film peels off, and the film becomes rough. As a result, the film became a film and peeled off.

It should be noted that the present invention is not limited to the above embodiment, and various changes and improvements may be made without departing from the scope of the present invention. For example,
According to the present invention, Ta, W, and Mo were used alone for the catalyst body, but instead, a composite material combining them was used, and a plurality of catalyst elements were added to the heat generating layer. You may.

[0078]

As described above, according to the present invention, in a resistor in which a polysilicon layer is formed on a substrate support by a catalytic CVD method, a catalytic element selected from Ta, W and Mo is 0.5 ppm. In the range of 10% to 10%, and
By containing the Group V element of the periodic table at an atomic ratio of 1.0 ppm to 0.3%, excellent heat generation can be obtained, and furthermore, it is inexpensive, has stable quality (adhesion, etc.) and can be mass-produced. An excellent resistor could be provided.

Further, according to the resistor of the present invention, the thermal
Heating part for head, heating part for inkjet, and half
Used as an antistatic coating for the electron beam mechanism of the conductor exposure equipment
Suitable as a protective coating for etching members (reactor).
Can be used. For example, a heating unit for inkjet and
As an antistatic coat for a semiconductor exposure apparatus, a specific resistance of 10 ^Three
-10⁰ (Ω · cm).

[Brief description of the drawings]

FIG. 1 is a sectional view of a resistor according to the present invention.

FIG. 2 is a diagram showing a schematic configuration of a catalytic CVD method according to the present invention.

FIG. 3 is an explanatory diagram showing a method for measuring the amount of warpage of a resistor.

[Explanation of symbols] 1 ... substrate 2, 4, ... electrodes 5 ... Vacuum container 6 ... Support 7 ... substrate for film formation 8 ... Gas introduction unit 9 Filament

Claims (1)

[Claims] 1. A resistor in which a polysilicon layer is formed on a substrate by a catalytic CVD method, wherein the catalytic body used in the catalytic CVD method is made of a catalytic element selected from Ta, W, and Mo. The catalyst element is added to the polysilicon layer by 0.5 pp.
A resistor characterized by containing an element of Group V of the periodic table at an atomic ratio of 1.0 ppm to 0.3% at an atomic ratio of m to 10%.