JPS6144402A - Wear resistant layer and electronic part - 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 I. BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to wear-resistant and electronic components having a wear-resistant layer. More specifically, it has high hardness, excellent abrasion resistance, and excellent heat resistance, and can be used as a retention layer for various devices, such as a thermal abrasion resistant layer for thermal printers used in facsimiles, etc. The present invention relates to an abrasion-resistant layer that can extend the life of an electronic component such as a thermal head that has a wear resistance of 1 M'kM.

PRIOR ART Conventionally, a thermal spatula P for a thermal printer used as one of the output methods for a facsimile machine, a computer terminal device, a printing device, a recording needle, etc. is composed of, for example, the structure shown in FIG. There is. That is, on the base 2 (via the heat storage glaze layer 3), the heat generating resistor layer 4 is formed, and on the other hand, the heat generating resistor 14 [i pair o re-)'+1g51
, 53 are ohmically connected.

Historically, a wear-resistant layer 6 is provided as the top layer in order to prevent wear and damage of the heating resistor layer 4 and the lead layers 51, 53 due to sliding contact with the thermal paper.

It is designed to conduct electricity to the heating resistor layer 4 through the IJ)9 layers 51, 53t+))l1 layer 51
．． The heat-generating resistor layer 4 in the 53rd area is made to generate heat, and this heat is applied via the wear-resistant layer 6 to the thermal paper that is in relative sliding contact with it, thereby performing thermal recording.

In such a thermal head, the wear-resistant layer 6 has high hardness, excellent wear resistance, and excellent heat resistance.
As a result, even after long-term sliding contact with thermal paper and repeated heat generation, the head retains its function, does not cause deterioration of the resistance value of the heat-generating resistor layer, and maintains the life of the head. required.

Therefore, in view of these points, the present inventors have previously proposed that a B-8i-P thin film is preferable as a wear-resistant layer for thermal heads, etc. (4? Application No. 55-21950). Etc.

The thin film according to the above proposal is formed by the OYD method,
It has excellent wear resistance and heat resistance.

However, this thin film still does not have sufficient abrasion resistance and heat resistance under the extremely harsh operating conditions of thermal spatula FK, and it has been repeatedly used over a long period of time under the load of running in contact with thermal paper. The heat generation causes, for example, a deterioration in the resistance of the heat generating resistor layer, eventually ending the life of the head, and further improvement of the wear-resistant layer characteristics is desired.

When forming the retaining layer of the thermal head on the base using the conventional OVD method, it is deposited at a high temperature of aOO to 900°C, so thermal stress at high temperatures may cause cracks to form as it is used or the resistance value to decrease. This is because it causes deterioration.

Note that if sputtering is used, the substrate heating temperature can be increased to 50°C.
Although the temperature can be lowered to 0° C. or lower, the layer will have a structure containing many cavities, and the mechanical strength and abrasion resistance of the layer will be significantly reduced.

■ Purpose of the Invention The purpose of the present invention is to obtain a thin thin film of a mixed gas containing B and P, and when used as a protective layer for electronic components such as those for thermal heads, to obtain a wear-resistant M that further improves the life of the head. 6. We are happy to provide this service.

Another object of the present invention is to provide a highly durable electronic component having this improved wear-resistant layer.

That is, the first invention is a wear-resistant layer characterized by comprising boron and phosphorus deposited by plasma decomposition of a mixed gas containing a boron compound and a phosphorus compound.

A second invention is a wear-resistant layer characterized by comprising boron, phosphorus, and 1 it% or less of hydrogen and/or halogen deposited by plasma decomposition of a mixed gas containing a boron compound and a phosphorus compound.

And the third invention is boron and phosphorus deposited by plasma decomposition of a mixed gas containing a boron compound and a phosphorus compound, or boron,
An electronic component characterized by having a wear-resistant layer consisting of phosphorus and hydrogen and/or halogen of lat% or less.

The wear-resistant layer of the present invention contains B and P.

In this case, the P content in the wear-resistant layer is 5 or less, in particular 0.001-1, relative to Bl, in atomic ratio.

When P/B exceeds 5 and special Kl, mechanical strength decreases,
Strength decreases with use.

Furthermore, when P/B is less than 0.001, the mechanical strength of the film decreases, resulting in insufficient wear resistance. First, cracks or peeling occur due to internal strain.

In addition to this twist and P, the wear-resistant layer may also contain H and/or hydrogen depending on the source used.

However, the amount of H or halogen is 1alX or less.

This is because if it exceeds 1 atX, the resistance decreases.

As mentioned above, the wear-resistant layer of the present invention contains B and P as essential components, and contains Hfiji and rogens as necessary. It may further contain other elements within the range of 1-fold f[z or less.

Such elements include Ge, 8n, Pb, and mant.

Examples include Zr and Nb.

The wear-resistant layer having such a composition takes an amorphous or polycrystalline form.

In this way, when a thin film layer consisting of the two essential components B and P and the above composition ratio is formed by glow discharge decomposition under the conditions described below, a hard film with homogeneous film quality and high mechanical strength and wear resistance can be formed. I can do it.

The film thickness may be determined as appropriate depending on the application, but it is usually 0.
-1 to lO, l1m, special KO, 5 to 10 μm.

The layer made of P is formed by a glow discharge decomposition (plasma decomposition) method.

Plasma decomposition may be performed by a radio frequency method or a microwave method.

When following the high frequency method, K is 1 to 301 V [) 1 g.

It is sufficient to input power of about 100 W to several XW.

Nine, when following the microwave law, IGHz to IOC
It is sufficient to input power of about 100 to 100 s.o.w.

The raw material gas used is boron hydride, such as BH,
, B, H, etc., boron halides such as Bot, ,
Phosphorus hydrides, e.g. PH, phosphorus halides, e.g. p
oz, etc. may be used.

Hydrogen, argon, helium, or the like, particularly hydrogen, may be used as the carrier, and the raw material gas may be introduced into the reaction system in a predetermined quantitative ratio.

Note that the operating pressure may be approximately 0.01 to 5 Torr, and the substrate temperature may be approximately 150 to 500°C.

Particularly preferably, the substrate temperature is 350 to 450° C., and the thin film formed in this temperature range has homogeneous film quality, high hardness, and good wear resistance.

Further, the film formation rate may be approximately 1 to 20 A/sec.

The abrasion-resistant layer formed in this way has high abrasion resistance and heat resistance, and when used as a protective layer for various devices, it can significantly improve the life of the device.

In particular, when the abrasion resistant layer of the present invention is used as an abrasion resistant layer for a thermal head, this effect becomes much more pronounced, and as the head is used, it becomes more difficult to wear under the load during thermal paper contact. Even when heating is performed over a very long period of time, the amount of deterioration in the resistance value of the heating resistor layer is significantly reduced, and the life of the head is significantly improved.

In such a case, a typical example of constructing a thermal head using the wear-resistant layer of the present invention may be carried out as follows.

That is, the substrate 2 may be made of ceramics such as alumina.

Furthermore, as shown in FIG. 1, the heat storage glaze layer 3 provided on one substrate 2 may be formed from a normal glass material. Note that the glaze layer 3 is similar to the normal case.
It is provided over almost the entire area on the board, and its thickness is 15~
20011rv, or may be formed from a glass-containing paste or slurry by a conventional method such as screen printing or dipping.

On the other hand, a heating resistor layer 4 is arranged on the glaze layer 3 as shown in FIG. The heating resistor layer 4 may be formed by any method, but
In view of its characteristics, a polycrystalline silicon thin film is preferable.

Also, this polycrystalline silicon thin film contains P and As.

Impurities such as B and 8b may be contained in an amount of about 100 weight X or less. And its resistance is 2
It may be about IO-'~5 x 10-30@d.

Alternatively, only one heating resistor 1 may be provided in a predetermined shape on the substrate, but usually, it is separated into many pieces and provided in a predetermined arrangement, for example, in the form of a thousand rows of strips. The thickness is generally 0.1 to 5 μm.

This heating resistor having a predetermined shape and a predetermined arrangement/P+
4, a pair of lead layers 51 and 53 are connected facing each other with a predetermined gap. The lead layer can be made of various metals,
Although it may be formed as a thin film according to various methods, it is preferably made of aluminum, gold, nickel, steel, tantalum, titanium, tungsten, molybdenum, or an alloy thereof, and furthermore, tungsten silicide, molybdenum silicide, or the like. In this case, the lead layer 51.5
3 may be located above the heating resistor layer 4 or may be located below it. Further, the thickness of the lead 1 may be approximately 0.5 to 2 μm.

The wear-resistant layer 1 of the present invention is applied as the top layer over almost the entire upper surface of the thermal head base as such a laminate.
56 are provided.

Above, we have described one typical example of configuring a thermal head, but in addition to this, various intervening layers may be provided in the thermal head, and as shown in 1, the part of the substrate corresponding to the heat generating part may be made into a convex shape. Needless to say, various embodiments are possible.

Further, the wear-resistant layer may have a two-layer structure, and the compositions of the upper layer and the lower layer may be changed.

(2) Specific Effects of the Invention The wear-resistant layer of the present invention is a very homogeneous film, and has extremely high wear resistance and heat resistance.

Therefore, the electronic component, especially the thermal head, having the wear-resistant layer of the present invention can provide a highly durable thermal head whose characteristics do not change over a long period of time.

Further, by utilizing such characteristics, it can be used not only as a thermal head but also as an abrasion resistant layer for devices such as rice balls to improve the life of the device.

For example, by taking advantage of its abrasion resistance, it is useful as an abrasion-resistant layer of a semiconductor photodetection head that is used in sliding contact with a transparent recording paper.

The inventor conducted various experiments to confirm the effects of the present invention. An example is shown below.

EXPERIMENTAL EXAMPLE A thermal head as shown in FIG. 1 was prepared to confirm the effects of the present invention.

First, the substrate 2 is 300 mm x 300 m.

Using 98% alumina with a thickness of 2 ml, 80%
A glaze layer 3 having a thickness of μm was formed. Then, according to chemical vapor deposition method, using silane and gelan as sources and hydrogen as carrier gas, a 1 μm film containing 1% by weight of boron was deposited.
A thick polycrystalline silicon thin film is deposited and photo-etched.
A plurality of polycrystalline silicon thin film heat generating resistors N4 were formed in the form of a thousand rows of 100 μm wide strips with a gap of 30 μm.

Thereafter, a W thin film with a thickness of 1.5 μm was deposited thereon, and a window of 100×230 μm was formed in the central portion K on each of the strip-shaped heating resistor layers 4 by photolithography. W lead layers 51 and 53 were formed in the same manner.

Next, an abrasion resistant layer of the present invention or a comparative one was applied over the entire surface of the eight types of thermal head underlayer laminates formed in this way to a thickness of 1 μm.

In this case, for heads B, O, D, and PK,
B, ) (, and PH, as sources, H! carrier, substrate temperature of 400°C, 13.56MH process 180
Glow discharge decomposition was performed at W, I Torr, and at that time, the flow rate ratio of each source was changed to form a wear-resistant layer.

When the composition of the obtained 94s thin film was analyzed by X-ray microanalyzer Augier spectroscopy and Esca, it was confirmed that it had the composition shown in Table 1 below.

Head B uses B, H, and PH3 as sources and performs vapor phase growth (CVN) at a substrate temperature of 900° C. with a Hll gear while changing the source flow rate ratio.

For the 96 types of heads A to F obtained in this way, a diode matrix was constructed according to a known method, and a pair of lead layers was attached to each heat generating resistor layer of the head while running the thermal paper in contact with it under normal pressure. through, at intervals of 10m1ac,
Pulse energization of 0.5 msec was repeated.

In this case, the applied power was set to the amount required for the saturation density of the thermal paper.

Pulse energization under such thermal paper running is 2X10'.
The resistance value deterioration (%) of all the heat generating layers was measured after that, and the results shown in Table 1 were obtained by averaging the results.

Table 1 Head Thin film retention MN composition Deposition method Resistance value deterioration "□-1 Nork B (invention) IB-0,01P 7' Lasma
35C (main 8A) IB-0, 01F-0
,5 Silk I 4 SD
B Leak B
1B-0,0IP CVD open FI IB-10P Prada i
Leak In this case, head B to which the present invention is applied
, O, the resistance degradation is less than 20%.

On the other hand, head D using a thin film retention layer having a composition other than the present invention
, F, a leak state occurs.

Claims (7)

[Claims] (1) A wear-resistant layer comprising boron and phosphorus deposited by plasma decomposition of a mixed gas containing a boron compound and a phosphorus compound. (2) The wear-resistant layer according to claim 1, wherein the atomic ratio of phosphorus/boron is 5 or less. (3) Boron, phosphorus, and 1^ deposited by glow discharge decomposition of a mixed gas containing boron compounds and phosphorus compounds
A wear-resistant layer characterized by comprising a^t% or less of hydrogen and/or halogen. (4) The wear-resistant layer according to claim 3, wherein the atomic ratio of phosphorus/boron is 5 or less. (5) It has a wear-resistant layer made of boron and phosphorus deposited by plasma decomposition of a mixed gas containing a boron compound and a phosphorus compound, or boron, phosphorus, and 1^a^t% or less of hydrogen and/or halogen. Featured electronic components. (6) Claim 5, wherein the electronic component is a thermal head having a glaze layer on a base, a heating resistor layer and an electrode layer on the glaze layer, and a wear-resistant layer as the top layer. Electronic components listed in section. (7) The electronic component according to claim 5 or 6, wherein the atomic ratio of phosphorus/boron is 5 or less.