JPH0232988B2 - - Google Patents
Info
- Publication number
- JPH0232988B2 JPH0232988B2 JP57000301A JP30182A JPH0232988B2 JP H0232988 B2 JPH0232988 B2 JP H0232988B2 JP 57000301 A JP57000301 A JP 57000301A JP 30182 A JP30182 A JP 30182A JP H0232988 B2 JPH0232988 B2 JP H0232988B2
- Authority
- JP
- Japan
- Prior art keywords
- value
- sioxny
- layer
- hardness
- wear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910020286 SiOxNy Inorganic materials 0.000 claims description 13
- 238000005299 abrasion Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N97/00—Electric solid-state thin-film or thick-film devices, not otherwise provided for
Landscapes
- Electronic Switches (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Non-Adjustable Resistors (AREA)
Description
本発明は、感熱記録ヘツドに係り、特に発熱抵
抗体を保護する耐摩耗層保護層に関するものであ
る。
従来薄膜形感熱記録ヘツドは、金属電極および
発熱抵抗体上に酸化タンタル（Ta2O5）、炭化シ
リコン（SiC）等の耐摩耗層を設けている。
しかし、Ta2O5は硬度が小さくて耐摩耗性が劣
るため、膜厚を厚くして実用する必要があり、
SiCは化学的に不安定で例ば感熱記録紙上の感熱
物質と反応を生じ耐摩耗性を著しく劣化させる。
一方、窒化シリコン（Si3N4）は硬度が大きく
化学的に安定であるが、薄膜状では膜の内部応力
が大きく亀裂を生じやすい欠点があつた。
これら三材料のヌープ硬度（耐摩耗性の指標と
なる）と、化合物の生成熱△H゜（安定性の指標と
なる）を表に示す。
The present invention relates to a thermal recording head, and more particularly to a wear-resistant protective layer that protects a heating resistor. Conventional thin film type thermal recording heads have a wear-resistant layer of tantalum oxide (Ta 2 O 5 ), silicon carbide (SiC), etc. on the metal electrodes and heating resistor. However, Ta 2 O 5 has low hardness and poor wear resistance, so it is necessary to make the film thicker for practical use.
SiC is chemically unstable and reacts with, for example, heat-sensitive substances on heat-sensitive recording paper, significantly deteriorating its abrasion resistance. On the other hand, silicon nitride (Si 3 N 4 ) has high hardness and is chemically stable, but in the form of a thin film, it has the disadvantage of high internal stress and a tendency to crack. The Knoop hardness (an indicator of wear resistance) and the heat of formation △H° (an indicator of stability) of these three materials are shown in the table.
【表】
Ta2O5は△H゜が−499.9であるため化学的に安
定であるが、その硬度はSi3N4の1/2以下である。
またSiCは硬度においては秀れた材料であるが、
△H゜が−26.7と余り大きくなく化学的に不安定で
ある。一方、Si3N4は硬度、△H゜は良好である
が、膜の内部応力が100Kg／mm以上と大きな圧縮
応力を持つている。
本発明の目的は、上記した従来技術の欠点のな
い硬度が大きくて耐摩耗性に秀れ、化学的安定性
が良く、かつ膜の内部応力が小さくて耐亀裂性の
良好な耐摩耗層を提供することにある。
そして本発明は耐摩耗層をシリコンオキシナイ
トライド（Si―Ｏ―Ｎ）とすることで達成され
る。
シリコンオキシナイトライドは、酸素含有量と
窒素含有量を変えることにより、SiO2に近い特
性を有するものからSi3N4に近い特性を有するも
のまで変化で変わり、その特性を所望の値に選択
できることを特徴としている。
シリコンナイトライドをSiOxNyで表わした場
合、ｘ、ｙの値が夫々0.2〜1.83、0.3〜1.3の範囲
のものが好ましい。そして、SiOxNy層は通常の
ドライプロセスで形成される。
以下、本発明を実施例により詳細に説明する。
実施例 １
第１図は感熱記録ヘツドの断面である。第１図
中、１はグレーズ層を設けたアルミナ基板、２は
厚さ0.15μm厚のCr―Si―Ｏの三元合金よりなる
発熱抵抗体層、３は厚さ1μmのAl電極、４は厚
さ4μmのSiOxNy（0.2＜ｘ＜1.83、0.3＜ｙ＜1.3）
層である。
図中の４〜６は、いずれもプラズマCV法で
行なつた。即ち反応性ガスとしてSiH4，NH3，
N2O5ガス，キヤリアーガスとしてN2ガスを導入
し、放電々力1.0KWで成膜した。
プラズマCVD法で形成したSiOxNy層のｘ，
ｙ値と、膜の内部応力の関係を第２図に、薄膜の
硬度との関係を第３図に示した。第２図で曲線５
はSiOxNyにおいてｘ値を0.5〜0.7としてｙ値を
変化させた場合、曲線６はSiOxNyでｙ値を0.6
〜0.8一定としてｘ値を変化させた場合の内部応
力変化を示す曲線である。
これからSiOxNy膜の内部応力はｙ値が増加す
るほど圧縮圧力が大きくなり、ｘ値に対しては16
〜30Kg／cm2の圧縮圧力で余り変化がない。また、
第３図で曲線７はSiOxNyでｘ値を0.5〜0.7とし
てｙ値を変化させた場合曲線８はSiOxNyでｙ値
を0.6〜0.8としてｘ値を変化させたときのヌープ
硬度を示している。第３図から、SiOxNy膜の硬
度はｘ値が増加するほど減少し、ｙ値が増加する
ほど増大することがわかる。
上記の方法で形成した発熱抵抗体について、実
印字寿命試験を行ない抵抗体保護層の耐摩耗性、
耐亀裂性を評価した。通電条件はパルス電圧印加
時間1.0msec，パルス周期10msecであり、発熱抵
抗体形状は幅90μm、長さ250μｍ、印加電力は
0.60W／抵抗体である。第４図に感熱紙による
SiCxNyの摩耗量を示す。曲線９はSiOxNyでｘ
値を0.5〜0.7としてｙ値を変化させた場合、曲線
１０はSiOxNyで値を0.6〜0.8としてｘ値を変化
させたときの摩耗量を示す。摩耗量は、従来品の
Ta2O5が1500Å／Kmに対し、本発明のものは1000
Å／Km以下である。
また膜の亀裂の発生については、第４図に示し
たSiOxNyでは走行30Kmで亀裂発生はない。また
発熱抵抗体の抵抗値の変化に対してもパルス印加
数5000万回後においても抵抗値変化率は初期抵抗
値に対して５％以内であり、抵抗体の酸化劣化等
に対しても良好な特性を示した。
以上述べたように本発明によれば、感熱紙によ
る耐摩耗層の摩耗量は1000Å／Km以下であるため
耐摩耗層の膜厚を減少でき、成膜時間を大幅に短
縮してスループツトを大きくすることができる。
また、従来使用されていた耐酸化保護層は不要
で、幅に製造原価低減がはかれる。[Table] Ta 2 O 5 is chemically stable because △H° is -499.9, but its hardness is less than half that of Si 3 N 4 .
Also, although SiC is an excellent material in terms of hardness,
△H° is -26.7, which is not very large and is chemically unstable. On the other hand, Si 3 N 4 has good hardness and △H°, but the internal stress of the film is 100 Kg/mm or more, which is a large compressive stress. The object of the present invention is to provide a wear-resistant layer that has high hardness, excellent wear resistance, good chemical stability, and low internal stress and good crack resistance without the drawbacks of the prior art described above. It is about providing. The present invention is achieved by using silicon oxynitride (Si-O-N) as the wear-resistant layer. By changing the oxygen content and nitrogen content, silicon oxynitride can be varied from having properties close to SiO 2 to properties close to Si 3 N 4 , and its properties can be selected to the desired value. It is characterized by what it can do. When silicon nitride is represented by SiOxNy, the values of x and y are preferably in the range of 0.2 to 1.83 and 0.3 to 1.3, respectively. Then, the SiOxNy layer is formed by a normal dry process. Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 FIG. 1 is a cross section of a thermal recording head. In Figure 1, 1 is an alumina substrate provided with a glaze layer, 2 is a heating resistor layer made of a ternary alloy of Cr--Si--O with a thickness of 0.15 μm, 3 is an Al electrode with a thickness of 1 μm, and 4 is an aluminum electrode with a thickness of 1 μm. 4μm thick SiOxNy (0.2<x<1.83, 0.3<y<1.3)
It is a layer. Items 4 to 6 in the figure were all carried out by the plasma CV method. That is, SiH 4 , NH 3 ,
N 2 O 5 gas and N 2 gas as a carrier gas were introduced, and a film was formed with a discharge force of 1.0 KW. x of the SiOxNy layer formed by plasma CVD method,
The relationship between the y value and the internal stress of the film is shown in Figure 2, and the relationship between the hardness of the thin film is shown in Figure 3. Curve 5 in Figure 2
Curve 6 is SiOxNy with an x value of 0.5 to 0.7 and a y value of 0.6.
This is a curve showing the internal stress change when the x value is changed while being kept constant at ~0.8. As for the internal stress of the SiOxNy film, the compressive pressure increases as the y value increases, and for the x value, 16
There is not much change at compression pressure of ~30Kg/ cm2 . Also,
In FIG. 3, curve 7 shows the Knoop hardness when SiOxNy is used with an x value of 0.5 to 0.7 and the y value is varied.Curve 8 shows the Knoop hardness when SiOxNy is used with a y value of 0.6 to 0.8 and the x value is varied. From FIG. 3, it can be seen that the hardness of the SiOxNy film decreases as the x value increases, and increases as the y value increases. The heating resistor formed by the above method was subjected to an actual printing life test to determine the wear resistance of the resistor protective layer.
Crack resistance was evaluated. The energization conditions are a pulse voltage application time of 1.0 msec, a pulse period of 10 msec, the shape of the heating resistor is 90 μm in width and 250 μm in length, and the applied power is
0.60W/resistor. Figure 4 is based on thermal paper.
Shows the wear amount of SiCxNy. Curve 9 is SiOxNy x
When the y value is varied from 0.5 to 0.7, curve 10 shows the wear amount when the x value is varied from 0.6 to 0.8 for SiOxNy. The amount of wear is the same as that of the conventional product.
While Ta 2 O 5 is 1500 Å/Km, the inventive one is 1000 Å/Km.
Less than Å/Km. Regarding the occurrence of cracks in the film, no cracks occurred in the SiOxNy shown in Figure 4 after traveling for 30 km. In addition, even after 50 million pulses have been applied to the resistance value of the heating resistor, the rate of change in resistance value is within 5% of the initial resistance value, which is good against oxidative deterioration of the resistor. showed characteristics. As described above, according to the present invention, the amount of abrasion of the abrasion resistant layer by thermal paper is less than 1000 Å/Km, so the thickness of the abrasion resistant layer can be reduced, the film formation time can be significantly shortened, and the throughput can be increased. can do. In addition, the oxidation-resistant protective layer used in the past is not required, which significantly reduces manufacturing costs.
第１図は感熱記録ヘツドの断面図、第２図，第
３図，第４図は本発明の感熱記録ヘツドの特性を
示す図である。
１…アルミナ基板、２…発熱抵抗体層、３…
Al電極、４…AiOxNy層。
FIG. 1 is a sectional view of a thermal recording head, and FIGS. 2, 3, and 4 are diagrams showing the characteristics of the thermal recording head of the present invention. 1... Alumina substrate, 2... Heat generating resistor layer, 3...
Al electrode, 4...AiOxNy layer.
Claims (1)
層と、この発熱抵抗体層上に設けられた耐摩耗層
よりなる感熱記録ヘツドにおいて、前記耐摩耗層
がSiOxNy（但し、0.2＜ｘ＜1.83；0.3＜ｙ＜1.3）
であることを特徴とする感熱記録ヘツド。1. In a thermal recording head consisting of a substrate, a heat generating resistor layer provided on the substrate, and an abrasion resistant layer provided on the heat generating resistor layer, the abrasion resistant layer is SiOxNy (where 0.2<x<1.83;0.3<y<1.3)
A heat-sensitive recording head characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57000301A JPS58118273A (en) | 1982-01-06 | 1982-01-06 | Heat-sensitive recording head |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57000301A JPS58118273A (en) | 1982-01-06 | 1982-01-06 | Heat-sensitive recording head |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58118273A JPS58118273A (en) | 1983-07-14 |
| JPH0232988B2 true JPH0232988B2 (en) | 1990-07-24 |
Family
ID=11470072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57000301A Granted JPS58118273A (en) | 1982-01-06 | 1982-01-06 | Heat-sensitive recording head |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58118273A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177633B1 (en) * | 1983-08-27 | 1989-10-11 | Alcatel N.V. | Electrothermal sheet recorder |
| JPS61215259A (en) * | 1985-03-19 | 1986-09-25 | 真空材料株式会社 | Manufacture of silicon nitride target for sputtering |
| JPS61277463A (en) * | 1985-06-04 | 1986-12-08 | Toshiba Corp | Thermal head |
| JPH0649375B2 (en) * | 1985-06-27 | 1994-06-29 | 京セラ株式会社 | Thermal head and method for producing the same |
| US4963893A (en) * | 1988-03-28 | 1990-10-16 | Kabushiki Kaisha Toshiba | Heat-resistant insulating substrate, thermal printing head, and thermographic apparatus |
| JPH0574645A (en) * | 1991-09-13 | 1993-03-26 | Hitachi Aic Inc | Chip type electronic parts |
| JP3205404B2 (en) * | 1992-09-28 | 2001-09-04 | ティーディーケイ株式会社 | Wear-resistant protective film and thermal head having the same |
| JPH06325967A (en) * | 1993-05-11 | 1994-11-25 | Nec Corp | Small-sized electronic component |
| JP4727555B2 (en) * | 2006-11-17 | 2011-07-20 | 株式会社アルバック | Lamination method of SiON film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365066A (en) * | 1976-11-22 | 1978-06-10 | Nec Corp | Semiconductor device |
| JPS5522863A (en) * | 1978-08-07 | 1980-02-18 | Nec Corp | Manufacturing method for semiconductor device |
| JPS56111680A (en) * | 1980-02-08 | 1981-09-03 | Toshiba Corp | Thermal head |
-
1982
- 1982-01-06 JP JP57000301A patent/JPS58118273A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365066A (en) * | 1976-11-22 | 1978-06-10 | Nec Corp | Semiconductor device |
| JPS5522863A (en) * | 1978-08-07 | 1980-02-18 | Nec Corp | Manufacturing method for semiconductor device |
| JPS56111680A (en) * | 1980-02-08 | 1981-09-03 | Toshiba Corp | Thermal head |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58118273A (en) | 1983-07-14 |
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