DE3618596A1 - Fluid-jet recording head, and recording system containing this fluid-jet recording head - Google Patents

Abstract

The fluid-jet recording head such as, for example, an ink-jet recording head, has fluid channels with fluid outlets, through which a recording fluid is released in the form of a droplet jet, and electricity/heat conversion elements for generating heat, which respond to electrical input signals and thus generate energy for the release of fluid. The electricity/heat conversion element has a heat-generating resistance film which consists of an amorphous material containing halogen atoms and hydrogen atoms in a matrix of carbon atoms. A recording system having this recording head is also described. The amorphous material can also contain silicon atoms and/or germanium atoms.

Description

The present invention relates to a liquid jet recording head and a liquid jet recording system including this liquid jet recording head.

Among the various recording systems known heretofore, there is one called an "ink jet recording system" The shockless system is excellent in that it can record at high speed on an ordinary sheet of paper made possible without significant noise occurring and some special fixing treatment is necessary.

Various proposals and improvements have been made in this type of recording system. Some of these suggestions and improvements have already been put into practice, while others are still in the process of being developed for practical use are.

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The ink jet recording system uses a recording liquid commonly referred to as "ink liquid". Droplets of the recording liquid are formed, which fly by various methods to the recording body, e.g., a sheet of paper, so that they are deposited on the recording body and thereby the desired information record.

The applicant of the present application also has a new one Proposed recording system of the inkjet type, which is described in DE-OS 28 43 064. This new method is based on the following principle. Thermal pulses are supplied as information signals to a recording liquid contained in a chamber. As a result of the supply of thermal impulses the ink generates vapor bubbles which in turn cause the ink to contract and pressurize so that it is discharged from the chamber. The recording liquid discharged in this way flies in the form of droplets against the recording body and is deposited thereon so as to record the information entered.

This system easily adapts to high speed recording and adjust color record because a high density multi-row arrangement can be created. Since furthermore this principle can be applied by a simpler arrangement than heretofore, the recording head can be made more compact as a whole and easily mass-produced. It is also to be noted that the recording head is effectively used IC and microprocessor technology, which have made remarkable advances, can be suitably long. For these reasons, this new liquid jet recording system is enjoying success wide application.

This liquid jet recording system mainly has a recording head that has an electricity / heat

Conversion element as a means for pressing out the ink and forming it contains droplets of liquid.

In order to achieve a highly effective introduction of thermal energy into the liquid and a good response behavior of the liquid in with respect to the on / off control of heat, the electricity / heat converting element is preferably in one with the dispensing opening communicating heating zone is provided so that the element can contact the liquid directly.

The electricity / heat conversion element consists essentially of a heat-generating resistance element which, when supplied generates heat with electrical energy, and a pair of electrodes through which the electrical energy is sent to the resistance element is fed.

This direct contact between the electricity / heat conversion element and the recording liquid, however, has the following disadvantages. The direct contact between the electricity-to-heat converting element and the liquid may drain depending on the resistivity of the liquid of the electric current through the recording liquid. The electric flowing through the liquid Electricity can cause electrolysis of the liquid. There is also a risk of a reaction between the heat-generating ones Resistance element and the liquid when the element is activated by the electrical energy supplied to it. Such Reaction can lead to corrosion of the heat-generating element, causing a change in resistivity and / or destruction of the heat-generating element results. It is also possible that the surface of the heat generating element is mechanically eroded or the element cracks or breaks as a result of a mechanical shock which occurs as a result of the action the vapor bubbles generated by the electrical energy collapse, to disappear.

In order to counteract this problem, it has been proposed that on the surface of the heat-generating element, which is made of an inorganic material excellent in properties required for heat-generating resistance, for example, an alloy such as NiCr, or metal borides such as ZrB ₂ and HfB ^, to form a protective layer from a material which has a high resistance _{to acids, such as SiO 2.} This protective layer is intended to protect the heat generating element from direct contact with the recording liquid in order to improve the reliability and durability in long-term use and thereby counteract the problems described above.

The liquid jet recording system with a recording head, containing this improved electrothermal converting element shows satisfactory applicability with respect to Acid resistance and durability when a liquid with relatively low electrical conductivity, e.g. one made with water and an alcohol as a solvent Liquid, serves as a colored recording liquid. However, this recording system has often failed to provide sufficient durability and to provide resistance to long-term changes when used with a recording liquid which has a high content of Na ions and therefore a high electrical Has conductivity. For this reason it was only possible to use this recording system with selected recording fluids and therefore it was not suitable for use in multicolor recording or natural color recording.

As mentioned above, the reliability and durability of the electrothermal converting element would be enhanced by the creation a protective layer on the heat generating element can be improved. In fact, it is very difficult to mass-produce to form such a protective layer with a high degree of reproducibility, and the protective layers thus produced tend to have defects which

desirably allow in the electrothermal conversion element to penetrate towards the heat generating element.

This problem is particularly serious with an arrangement known as a "high density multiple orifice" which uses a fluid channel or a liquid nozzle having a plurality of heating sections arranged in high density is provided. Such Namely, the arrangement requires that numerous electricity-to-heat converting elements corresponding in number to the number of the liquid nozzles are provided be formed at the same time. Therefore, any caused due to a failure of the protective layer Failure of an electricity / heat conversion element is serious Problem from the point of view of the yield of the recording system as well as the production cost. Furthermore, the protective layer tends in addition, the thermal response and the heat generation capacity to deteriorate in response to the input electrical signals.

Under the circumstances, there is an increasing demand for the development of a liquid jet recording system Use of an electricity / heat conversion element without a protective layer, so that the heat generating element is directly exposed to the recording liquid, but the electricity / The heat conversion element is highly resistant to heat, acid, mechanical shock and electrochemical conversion and exhibits excellent thermal responsiveness.

Accordingly, it is an object of the invention to provide a liquid jet recording head and a liquid jet recording system with such a recording head improved so as to be those described above, the Overcoming problems inherent in the prior art.

It is intended to provide a liquid jet recording head and a liquid jet recording system with such a recording

tion head can be provided, the liquid jet recording head has a heat generating resistance element which has high chemical resistance as well as high resistance to electrochemical conversion, acid, mechanical shock and heat shows, so that the protective layer on the heat-generating Resistance element can be omitted and a better thermal Responsiveness is guaranteed.

Also intended is a liquid jet recording head and a liquid jet recording system including the same Recording head can be provided in which the liquid jet recording head has a heat generating element which is easy to form and excellent in mechanical strength and has softness as well as high chemical resistance.

Also intended is a liquid jet recording head and a liquid jet recording system having such There can be provided a recording head in which the recording head includes a heat generating element excellent in resistance is controllable.

Finally, a liquid jet recording head and a liquid jet recording system with a such a recording head can be provided in which the recording head has a heat generating resistance element, that easily has excellent heat accumulation and heat radiation property as well as various desirable properties such as bonding between the substrate and the Resistance film, resistance to chemical reaction, etc.

To this end, according to one aspect of the invention, there is provided a liquid jet recording head comprising at least a liquid outlet for the delivery of a recording liquid for the purpose of forming a jet of droplets of the recording liquid and at least one electricity / heat conversion

element for generating heat energy and forming the droplets of the recording liquid, whereby the electricity / Heat converting element is a heat generating resistive film which consists of a halogen atom and hydrogen atoms in a matrix of carbon atoms, amorphous material. It also becomes a liquid jet recording system in which this recording head is built.

According to another aspect of the invention, there is a jet of liquid -Recording head created with at least one liquid drop outlet for the delivery of a recording liquid in the form of a jet of recording liquid droplets, at least one liquid passage communicating with the outlet and having a heating section, and at least one electricity-to-heat converting element corresponding to the heating section, the one formed on a substrate, heat-generating resistive film made of a halogen atom and hydrogen atom in a matrix of carbon atoms, amorphous material and a pair of electrodes electrically connected to the heat generating resistor film. It will there is also provided a liquid jet recording system incorporating this recording head.

The foregoing and other objects, features, and advantages of the invention will become apparent from the following description of US Pat preferred embodiment clearly if you read them with reference to the accompanying drawing.

Fig. 1 is a partial view of the recording head according to an embodiment of the present invention;

Fig. 2 is a section on the line H-II of Fig. 1; Fig. 3 is a section on the line III-III of Fig. 2;

_ ₁₅ _ 3613596

Figs. 4 and 5 are partial sections showing different examples of an arrangement of the electrothermal converting elements in the recording head of the invention;

Figure 6 is a schematic representation of the deposition system;

Figures 7 and 8 are perspective, partly in section Partial views of the recording head according to FIG of the present invention;

9 to 12 are partial sections of different examples the recording head of the present invention;

Figs. 13, 15 and 17 are perspective views of various Examples of the arrangement of electricity-to-heat converting elements in the recording head of the present invention;

Figures 14, 16 and 18 are sectional views of the examples of the arrangements shown in Figures 13, 15 and 17;

19 is a perspective view of a top plate the recording head of the present invention;

Figs. 20, 21 and 22 are perspective views of various Examples of the recording head of the present invention;

Figure 23 is a perspective view of one of the present invention Ink jet recording system;

Figures 24 through 29 are graphs illustrating the Distribution of the content of halogen atoms and / or of the substance controlling the electrical conductivity in a heat-generating one Show resistance film; and

Fig. 30 is a perspective view of a recording system of the present invention with the wall partially removed.

The invention is fully described below with reference to the accompanying drawing.

Referring to Figures 1 and 2, a heat generating resistive film 14 is used as a constituent part of an electrothermal converting element carried by a substrate 12. On the heat generating resistor film 14, a pair of electrodes 16, 17 are provided. As can be seen from Fig. 1, a plurality of modules are each composed of the heat generating resistor film 14 and that on the layer 14 provided electrodes 16, 17 arranged side by side, so that a plurality of effective heat generating zones 18, 18 ', 18' 'are created which are arranged with regular intervals. In the embodiment described, the electrodes are 16 of the modules are connected to a common line so that they form a common electrode. The arrangement is such that the Heat generating zones 18, 18 ', 18 "independently by the electrodes 16,17 are supplied with electrical signals so that these zones generate heat in a controlled manner. From the 2 and 3 it can be seen that a cover plate 20 with the heat generating zones 18, 18 ', 18' 'opposite channels 22, 22 ', 22 "is attached to the overall body defined by the substrate 12, the heat generating resistor film and the electrodes 16,17 is formed. The channels extend in the direction of the Line II-II in Figure 1, as clearly shown in Figure 3, which is a section along the line III-III of FIG. These channels create liquid passages which are the spaces for containing the recording liquid. Any of these fluid passages has a heating section 24 that gives off heat to the recording liquid in the liquid passage.

Each of the fluid channels is open at its left end, as shown in Figure 2 at 26. The open end 26 therefore forms

an exit for the recording liquid. The other end of the liquid channel, i.e. the right end in Figure 2, stands with the source of the recording liquid. The arrangement is such that when a recording signal is supplied responsive heat generation by the heat generating zone connected to one of the liquid channels, the recording liquid evaporated in the liquid channel with the formation of vapor bubbles is so as to increase the pressure of the recording liquid and discharge the liquid standing at the outlet 26 from the outlet, as indicated by the arrow X in FIG. As can be understood from the preceding explanation, the figure is absent the representation of the cover plate 20.

Preferably, but not necessarily, there is Substrate 12 made of a material with a high durability to the heat generated during the formation of the heat-generating Resistive film 14 on the substrate is transferred to this, as well as to heat generated by the during operation Layer 14 is generated. The material of the substrate 12 also preferably has a higher specific electrical resistance than the heat generating resistance film 14 formed thereon, however, this is not essential, and the resistivity of the Substrate 12 may be smaller than that of the heat generating resistor film 14 when between the substrate 12 and an insulating layer is disposed on the heat generating resistor film 14 is. The material of the substrate 12 can have a high or a low thermal conductivity, depending on the conditions among which the liquid jet recording head is applied.

Typical examples of substances usable as the material of the substrate 12 in the invention are inorganic Materials such as glasses, ceramics, silicon and metals, and organic materials such as polyamide resins and polyimide resins.

The heat generating resistor film 14 is made of an amorphous material which contains halogen atoms and hydrogen atoms in one Contains matrix of carbon atoms. As the halogen atoms, F, Cl, Br and J atoms, etc. are alone or in the form of a mixture suitable. Among these halogens, F and Cl are preferred, and among these, F is most preferred.

According to the invention, the halogen atoms and hydrogen atoms amorphous material contained in a matrix of carbon atoms furthermore contain silicon atoms.

According to the invention, the halogen atoms and hydrogen atoms amorphous material contained in a matrix of carbon atoms also contain germanium atoms.

According to the invention, the halogen atoms and hydrogen atoms amorphous material contained in a matrix of carbon atoms furthermore contain silicon atoms and germanium atoms.

Any of the amorphous materials discussed above, viz the amorphous material containing halogen atoms and hydrogen atoms in a matrix of carbon atoms, the halogen atoms, Hydrogen atoms and silicon atoms in a matrix of carbon atoms Amorphous material containing halogen atoms, hydrogen atoms and germanium atoms in a matrix of carbon atoms containing amorphous material, and the amorphous material containing halogen atoms, hydrogen atoms, silicon atoms and germanium atoms, may further contain, according to the present invention, a substance which controls the electrical conductivity of the heat-generating resistive film.

The substance that controls electrical conductivity may be a so-called impurity in the semiconductor field, e.g. a p-type impurity that gives p-conductivity, or an η-type impurity that imparts η conductivity.

Examples of p-type impurities are Group III elements of the periodic table such as B, Al, Ga ₅ In, Tl ₅ , etc., among which B and Ga are particularly preferred, while examples of η-type impurities are the elements of Group V of the Periodic Table are, such as P _5, As, Sb and Bi, of which P and As are most preferred. These elements can be used alone or in combination with one another.

The content of halogen atoms and / or hydrogen atoms in the heat generating resistance film 14 can be directed in the direction of Film thickness may be unevenly distributed. In particular, the distribution of the halogen atoms and / or the hydrogen atoms in the direction the thickness form such a gradient that the content towards the top of the film 14 or vice versa towards the bottom of the film 14 towards, i.e. the side adjacent to the substrate 12, increases. Furthermore, the distribution can be such that the content along the thickness of the Film 14 has a maximum value or a minimum value. Accordingly, the distribution of the content of halogen atoms and / or of hydrogen atoms in the direction of the thickness of the heat generating resistor film 14 are appropriately selected, so that the desired properties are created.

When the heat generating resistor film has 14 silicon atoms, Contains halogen atoms and hydrogen atoms, at least one of these three kinds of atoms may be in the direction of the thickness of the heat-generating Resistance film 14 have an uneven distribution. In particular the distribution of at least one of the three types of atoms can have such a gradient that the content towards the top of the Film 14 progressively increases or, conversely, increases towards the underside of film 14, i.e. the side adjacent to substrate 12. The distribution pattern can also be such that the content at least one of these three types of atoms along the thickness of the film 14 has a maximum or a minimum value. The distribution pattern the content of at least one of the three kinds of atoms along the thickness of the heat generating resistor film 14 can be suitably so

be chosen so that the desired properties are created.

If the heat generating resistive film has 14 germanium atoms, Contains halogen atoms and hydrogen atoms, at least one of these three kinds of atoms may be in the direction of the thickness of the heat-generating Resistance film 14 have an uneven distribution. In particular the distribution of at least one of the three types of atoms can have such a gradient that the content towards the top of the Film 14 progressively increases or, conversely, increases towards the underside of film 14, i.e. the side adjacent to substrate 12. The distribution pattern can also be such that the content at least one of the three types of atoms along the thickness of the film 14 has a maximum or a minimum value. The distribution pattern the content of at least one of the three kinds of atoms along the thickness of the heat generating resistor film 14 can be appropriately selected that the desired properties are created.

When the heat generating resistor film has 14 silicon atoms, Contains germanium atoms, halogen atoms and hydrogen atoms, at least one of these four kinds of atoms can be in the direction of the thickness of the heat generating resistive film 14 have an uneven distribution. In particular, the distribution can be at least one of the four Types of atoms have such a gradient that the content increases progressively towards the top of the film or vice versa towards the bottom of the film 14, i.e. the side adjacent to the substrate 12, increases. The distribution pattern can also be such that the content at least one of these four types of atoms along the thickness of the film 14 has a maximum or a minimum value. The distribution pattern of the salary at least one of the four kinds of atoms along the thickness of the heat generating resistor film 14 can be appropriately selected so that that the desired properties are created.

When the heat generating resistance film 14 has the electrical Conductivity-controlling substance, e.g. when the Film 14 Halogen atoms, hydrogen atoms and the electrical conduction

ability-controlling atoms can contain at least one of these three kinds of atoms are unevenly distributed in the direction of the thickness of the heat generating resistor film 14. In particular the distribution of at least one of the three types of atoms can have such a gradient that the content towards the top of the Film increases progressively or, conversely, increases towards the underside of the film 14, i.e. the side adjacent to the substrate 12. The distribution pattern can also be such that the content of at least one of these three types of atoms along the thickness of the film 14 has a maximum or has minimum value. At least the distribution pattern of the salary one of the three kinds of atoms along the thickness of the heat generating resistor film 14 can be appropriately selected so that the desired properties are created.

This also applies to other cases, namely a first case in which the heat generating resistor film is silicon atoms, halogen atoms, hydrogen atoms and an electric one Contains conductivity controlling substance, one second case in which the heat generating resistance film 14 has germanium atoms, halogen atoms, hydrogen atoms and one the electric Contains conductivity controlling substance, and a third case where the heat generating resistive film 14 Silicon atoms, germanium atoms, halogen atoms, hydrogen atoms and contains a substance that controls electrical conductivity. So in all of these cases the above mentioned may be different Combinations of the constituent elements one uneven distribution of the content of at least one of the constituents elements are accepted, and the distribution pattern of the constituent element or the constituent element can be in be selected appropriately so that the desired properties are achieved.

Figures 24 to 29 show practical examples of the distribution pattern of the content of at least one of the silicon, Germanium, halogen and hydrogen atoms and the electric

Conductivity controlling substance along the thickness of the heat generating resistive film 14. In these figures, the axis of ordinate represents the distance T from the interface between the substrate 12 and the heat generating resistor film 14 and the thickness t of the heat generating resistor film 14 while the abscissa axis the content C of at least one of the silicon, Germanium, halogen and hydrogen atoms and the substance that controls electrical conductivity. In these figures the axes C and T are varied so that the peculiarities these figures are emphasized. The invention can according to the distribution patterns indicated in these figures within certain tolerance ranges of the values can be carried out in the relevant cases.

It is clear to the person skilled in the art, however, that the distribution patterns of the content given in these figures are for illustration only the invention does not exclude other distribution patterns. The distribution patterns the contents of the various constituent elements can differ from each other and to achieve the desired one Properties can be selected independently of each other. The thickness of the heat generating resistor film 14 can be freely selected, so that optimal thermal and mechanical properties are created.

The content of halogen atoms in the heat generating resistor film 14 is preferably in the range of 0.0001 to 30 atom%, in the more preferred cases between 0.0005 and 20 atom% and especially between 0.001 and 10 atom%, although this content can be selected as desired in order to achieve the required properties.

The content of hydrogen atoms in the heat generating Resistive film 14 is preferably in the range of 0.0001 to 30 atomic percent, in more preferred cases between 0.0005 and 20 atom% and especially between 0.001 and 10 atom%, although

this salary can be selected as desired to make the required To achieve properties.

The sum of the contents of the halogen atoms and the hydrogen atoms in the heat generating resistor film 14 is preferably in the range from 0.0001 to 40 atomic%, in the more preferred cases between 0.0005 and 30 atomic% and especially between 0.001 and 20 atomic percent, although these contents are selected as desired can be in order to achieve the properties corresponding to the requirement.

The content of any silicon atoms present in the heat-generating Resistance film 14 is preferably in the range between 0.0001 and 40 atomic percent, in the more preferred cases between 0.0005 and 20 atom% and in particular between 0.001 and 10 atom%, although this level can be selected as desired to obtain the required properties.

The content of any germanium atoms present in the heat generating resistor film 14 is preferably in that Range between 0.0001 and 40 atom%, in the more preferred cases between 0.0005 and 20 atom% and in particular between 0.001 and 10 atomic percent, although this content can be selected as desired to achieve the required properties.

If the halogen atoms, hydrogen atoms and silicon atoms are included, the sum of the contents of the silicon, Halogen and hydrogen atoms in the heat generating resistor film 14 preferably in the range between 0.0001 and 40 atom%, in the more preferred cases between 0.0005 and 30 atom% and in particular between 0.001 and 20 atom%, although this content can be selected as desired in order to achieve the required properties.

When the halogen atoms, hydrogen atoms and the germanium atoms are contained, the sum of the contents of germanium, halogen and hydrogen atoms in the heat generating resistor film 14 is preferably in the range between 0.0001 and 40 atomic%, in the more preferred cases between 0.0005 and 30 atom% and in particular between 0.001 and 20 atom%, although this content can be selected as desired in order to achieve the required properties.

When the halogen atoms, hydrogen atoms, silicon atoms and the germanium atoms are contained, the sum of the contents of the silicon, germanium, halogen and hydrogen atoms is in the heat-generating one Resistive film 14 preferably in the range between 0.0001 and 40 atomic percent, in more preferred cases between 0.0005 and 30 atomic percent, and especially between 0.001 and 20 atomic percent, although this content can be selected as desired to achieve the to achieve the required properties.

The content of any present, the electrical Conductivity controlling substance in the heat generating resistive film 14 is preferably in the range of 0.01 to 50,000 atomic ppm, in the more preferred cases between 0.5 and 10,000 atomic ppm and in particular between 1 and 5000 atomic ppm, although this level can be determined as desired to achieve the required properties. The areas mentioned above the contents of the constituent elements apply both to the case that the elements are evenly distributed and to in the event that these elements are unevenly distributed.

The thickness of the heat generating resistance layer is not particularly limited; any desired thickness can be chosen to achieve the desired thermal and mechanical properties.

As mentioned above, in the recording head of the invention, the heat generating resistor film 14 is made of an amorphous material containing halogen atoms and hydrogen atoms in a matrix of carbon atoms. This amorphous material is hereinafter expressed as "aC: (X ₅ H)", wherein X indicates halogen atoms while H indicates hydrogen atoms. The amorphous material aC: (X, H) can be formed by the plasma CVD method such as the glow discharge method or by a vacuum deposition method such as sputtering.

The method of forming the resistance _{layer 14 of aC: (X 5} H) by the glow discharge method basically comprises the steps of introducing the substrate 12 into a deposition chamber with internal negative pressure and introducing a material gas capable of supplying carbon atoms C, one for supplying Material gases capable of delivering halogen atoms X and a material gas capable of supplying hydrogen atoms H into the deposition chamber, a glow discharge being carried out in the deposition chamber by means of high-frequency waves or microwaves, whereby an aC: (X ₅ H) -FiIm is formed on the substrate 12. The rate of introduction of the X material gas and / or the H material gas can be changed with time during the glow discharge when an uneven distribution of the halogen atoms X and / or the hydrogen atoms H is required.

On the other hand, the formation of the resistance film 14 of aC: (X ₅ H) is carried out by sputtering according to a method which basically comprises the steps of placing the substrate 12 in a deposition chamber in which a negative pressure atmosphere of an inert gas such as Ar, He or its mixture, is maintained, and performing sputtering on a target composed of carbon atoms C while introducing the X material gas for supplying the halogen atoms and the H material gas for supplying the hydrogen atoms H. The rate of introduction of the X gas and / or the Η gas can be timed

can be varied during the atomization to a certain gradient, i.e. to achieve a non-uniform distribution of the halogen atoms X and / or the hydrogen atoms.

The heat generating resistor film 14 in the recording head of the invention may be made of an amorphous material containing silicon atoms in a matrix of carbon atoms in addition to halogen atoms and hydrogen atoms. This amorphous material is hereinafter referred to as "aC: Si: (X, H)", wherein Si represents silicon atoms, X represents halogen atoms, and H represents hydrogen atoms. The amorphous material aC: Si: (X ₅ H) can be formed by a plasma CVD method such as a glow discharge method or a vacuum deposition method such as sputtering.

The method of forming the resistive layer 14 of aC: Si: (X ₅ H) by the glow discharge method basically comprises the steps of introducing the substrate 12 into a deposition chamber under reduced internal pressure and introducing a material gas capable of supplying carbon atoms C, one for supply A material gas capable of supplying halogen atoms X and a material gas capable of supplying hydrogen atoms H into the deposition chamber, while a glow discharge is performed in the chamber by high frequency waves or microwaves, whereby an aC: Si: (X, H) -FiIm is formed on the substrate 12 . The rate of introduction of at least one of the Si material, X material and H material gases can be varied over time during the glow discharge if an uneven distribution of the Si atoms, X atoms and Η atoms is sought.

On the other hand, the formation of the resistance film 14 of aC: Si: (X ₅ H) is carried out by sputtering by a method which basically involves the steps of introducing the substrate 12 into a deposition chamber in which one is formed by an inert gas such as Ar, He or their mixture maintain a negative pressure atmosphere formed

and performing sputtering on a target formed by the carbon atoms C while the Si material gas for supplying the silicon atoms Si, the X material gas for supplying the halogen atoms X and the H material gas for supplying of the hydrogen atoms H are introduced. The speed of introduction at least one of Si material, X material, and H-material gases can be varied in time during the atomization, an uneven distribution of at least one of the Si atoms, Get X atoms and Η atoms.

The heat generating resistive film 14 in the recording head of the invention may be made of an amorphous material such as contains germanium atoms in a matrix of carbon atoms in addition to halogen and hydrogen atoms. This amorphous material will hereinafter referred to as "a-C: Ge: (X, H)", wherein Ge indicates germanium atoms, X halogen atoms, and H hydrogen atoms. The amorphous material a-C: Ge: (X, H) can be produced by the plasma CVD method such as the Glow discharge process, or by a vacuum deposition process, such as atomization.

The method of forming the resistive layer 14 of aC: Ge: (X, H) by glow discharge basically comprises the steps of placing the substrate 12 in a deposition chamber under reduced internal pressure and introducing a gaseous material capable of supplying carbon atoms C, one for supplying the Germanium atoms Ge capable gas material, a gas material capable of supplying the halogen atoms X and a gas material capable of supplying the hydrogen atoms H into the deposition chamber, while a glow discharge is triggered in the chamber by high frequency or microwaves and thereby a film of aC on the substrate 12: Ge: forms (X ₅ H). The rate of introduction of at least one of the Ge ₃ X and H gas materials may be changed with time during glow discharge when uneven distribution of at least one of the germanium atoms Ge, halogen atoms X and hydrogen atoms H is required.

On the other hand, the formation of the resistor film 14 of a-C: Ge: (X, H) is carried out by sputtering by a method which basically comprises the following stages: arrangement of the substrate 12 in a deposition chamber in which a negative pressure atmosphere from an inert gas such as Ar, He or their mixture, is maintained, and carrying out the atomization on one by the carbon atoms formed target, while the Ge gas material for delivery of the germanium atoms Ge, the X-gas material for delivery the halogen atoms X and the H gas material for supplying the Hydrogen atoms H are introduced. The rate of introduction of at least one of the Ge, X and H gas materials can be can be varied in time during the sputtering in order to avoid an uneven distribution of at least one of the germanium atoms Ge, halogen atoms X and hydrogen atoms H to get.

The heat generating resistor film 14 in the recording head of the invention may be made of an amorphous material containing silicon atoms and germanium atoms in a matrix of carbon atoms in addition to halogen and hydrogen atoms. This amorphous material is hereinafter referred to as "aC-Si: Ge: (X ₅ H)", wherein Si indicates silicon atoms, Ge Germanium atoms, X halogen atoms, and H hydrogen atoms. The amorphous material aC: Si: Ge: (X ₅ H) can be formed by the plasma CVD method such as the glow discharge method or by a vacuum deposition method such as sputtering.

The method of forming the resistive layer 14 of a-C: Si: Ge: (X, H) by glow discharge basically comprises the steps the placing of the substrate 12 in a deposition chamber under reduced internal pressure and the introduction of a for supplying Carbon atoms C capable gas material, one for delivery of the silicon atoms capable of gaseous material, one for delivery of germanium atoms capable of gaseous material, one gaseous material capable of supplying halogen atoms X and one of supplying of the hydrogen atoms H capable gas material in the deposition

chamber, while a glow discharge is triggered in the chamber by high-frequency waves or microwaves, thereby forming a film of aC: Si: Ge: (X ₁ H) on the substrate 12. The introduction rate of at least one of Si, Ge, X and H gas materials may be changed with time during glow discharge when uneven distribution of at least one of silicon atoms Si, germanium atoms Ge, halogen atoms X and hydrogen atoms H is required.

On the other hand, the formation of the resistor film 14 of a-C: Si: Ge: (X, H) is carried out by sputtering by a method which basically comprises the following stages: placing the substrate 12 in a deposition chamber in which a negative pressure atmosphere from an inert gas such as Ar, He or their mixture, is maintained, and carrying out the atomization on one by the carbon atoms formed target, while the Ge gas material for the delivery of the germanium atoms, the Si gas material for the delivery the silicon atoms Si, the X gas material for supplying the halogen atoms X and the H gas material for supplying the hydrogen atoms H to be introduced. The rate of introduction of at least one of the Si, Ge, X, and H gas materials can be varied during atomization be varied over time in order to avoid a non-uniform distribution of at least one of the silicon atoms Si, germanium atoms Ge, halogen atoms X and hydrogen atoms H to reach.

According to the invention, any of the amorphous materials mentioned above can be used. aC: (X ₅ H), aC: Si: (X ₅ H), aC: Ge: (X, H) and aC: Si: Ge: (X, H) also contain a substance that controls electrical conductivity. These amorphous materials are hereinafter referred to as "aC: (X, H) (p, n)" ₅ "aC: Si: (X, H) (p, n) ⁿ ," aC: Ge: (X, H) (p , n) "and" aC: Si: Ge: (X, H) (p, n) "denotes, where (p, n) represents the electrical conductivity controlling substance. These amorphous materials with the electrical conductivity controlling substance can also by the plasma CVD method such as glow discharge, or by a vacuum deposition method such as

Atomization, will be formed.

Examples of methods of forming the heat generating resistive film 14 are given below with particular reference to an a-C: (X, H) (p, n) type material. It should be noted, however, that these procedures work in the same way as well can be applied to the other amorphous materials containing an electrical conductivity controlling substance.

The method of forming the resistive layer 14 from a-C: (X, H) (p, n) by glow discharge basically comprises the steps placing the substrate 12 in a deposition chamber under reduced internal pressure and introducing one for delivery of the carbon atoms C capable gas material, one for delivery the gas material capable of supplying halogen atoms, a gas material capable of supplying hydrogen atoms H, and one of supplying the substance that controls electrical conductivity into the deposition chamber, while a glow discharge is initiated in the deposition chamber by high frequency waves or microwaves and thereby forming a film of a-C: (X, H) (p, n) on the substrate 12. The speed of introduction of at least one of the X, H and (p, n) gas materials can be varied over time during the glow discharge if an uneven distribution at least one of the halogen atoms X, hydrogen atoms H and the substance (p, n) is required.

On the other hand, the formation of the resistor film 14 of a-C: (X, H) (p, n) is carried out by sputtering by a method which basically comprises the following stages: placing the substrate 12 in a deposition chamber in which a negative pressure atmosphere from an inert gas such as Ar, He or their mixture, is maintained, and carrying out the atomization on one by the carbon atoms formed target while the X gas material to supply the halogen atoms X, the H gas material for introduction the hydrogen atoms H and the (p, n) gas material for delivery

the electrical conductivity controlling substance in the chamber is inserted. The rate of introduction of at least one of the X, H and (p, n) gas materials can be timed be varied to at least an uneven distribution one of the halogen atoms X, hydrogen atoms H and the electrical Conductivity-controlling substance to achieve.

It is possible to make a remarkable improvement in the resistance to chemicals and in the flexibility of the to achieve heat generating resistive film 14 in that one of the amorphous composition of the a-C: (X, H) -type silicon atoms Si and germanium atoms Ge added. It should also be noted that the controllability of the resistance of the heat generating Resistance film by incorporating the electrical conductivity controlling substance improved in a remarkable way can be.

In the processes outlined above, the material can gas to supply the carbon atoms (C), the halogen atoms (X), the hydrogen atoms (H) and the electrical conductivity-controlling substance (p, n) be substances that are under normal pressure present in gaseous form or gasified under a reduced pressure can be.

The material for supplying the carbon atoms (C) may include saturated hydrocarbons having 1 to 5 carbon atoms, ethylenic hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, and aromatic hydrocarbons. Practical examples of saturated hydrocarbons are methane (CH,), sthan (C _? H _g ), propane (C ₃ H ₈ ), η-butane (n-CJ-Lg) and pentane (C ₅ H ₁₂ ). Practical examples of ethylenic hydrocarbons are ethylene (C _? H-), propylene (C ₃ H ₅ ), butene-1 (C ₄ H ₈ ), butene-2 (C ₄ H ₃ ), isobutylene (C ₄ H ₃ ) and Pentene (Cj-H-iq). Practical examples of acetylenic hydrocarbons are acetylene (C ₂ H ₂ ), methyl _{acetylene (C 3} H ₄ ) and

Butyne (CH _fi ). A practical example of an aromatic hydrocarbon is benzene (CgHg).

Examples of the material for the supply of silicon atoms Si are silicon hydrides (silanes) such as SiH, Si 'H _g, Si ₃ Hg and Si ₄ H _10, and silicon halides (substituted by halogen atoms silane derivatives) such as SiF, (SIFP) ₅₅ (SiFp) ₆ , (SiFp) ₄ , SipFg, Si ₃ F ₈ , SiHF ₃ , SiH ₂ F ₂ , SiCl ₄ , (SiCl ₂ J ₅ , SiBr ₄ , (SiBr ₂ J ₅ , Si ₂ Cl ₆ and SIpCl ₃ F ₃ .

Examples of the material for supplying germanium atoms Ge are germanium hydrides such as GeH ₄ , Ge ₂ Hg, Ge ₃ Hg, Ge ₄ H ₁₀ , GepH.p, Ge _fi H, ₄ , Ge ₇ H, _fi , Ge ^ Hg and GeqH _{? 0} , and germanium halides (germanium hydride derivatives substituted by halogen atoms), such as GeF _{4 , (GeF 2} ) ₅ , (GeF ₂ J ₆ , (GeFpJ ₄ , Ge ₂ F ₆ , Ge ₃ F ₃ , GeHF ₃ , GeH ₂ F ₂ , GeCl ₄ , (GeCl ₂ ) ₅ , GeBr ₄ , (GeBr ₂ J ₅ , Ge ₂ Cl ₅ and Ge ₂ Cl ₃ F ₃ .

The materials for supplying the halogen atoms X include halogens, halides, interhalogen compounds, and halogen-substituted hydrocarbon derivatives. Practical examples of halogens are Fp, CIp, Br _? and J_. Practical examples of halides are HF, HCl, HBr and HJ. Practical examples of interhalogen compounds are BrF, ClF, ClF ₃ , BrF ₅ , BrF ₃₅ JF ₃ , JF ₇ , JCl and JBr. Practical examples of halogen-substituted hydrocarbon derivatives are CF ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CCl ₄ , CHCl ₃₅ CH ₂ Cl ₂ , CH ₃ Cl, CBr ₄ , CHBr ₃ , CH ₂ Br ₂ , CH ₃ Br, CJ ₄ , CHJ ₃ , CH ₂ J ₂ and CH ₃ J.

The materials for supplying the hydrogen atoms H include hydrogen gas and also saturated hydrocarbons, Ethylenic hydrocarbons, acetylenic hydrocarbons and aromatic hydrocarbons, which are also used as material for the Introduction of carbon atoms serve.

Examples of the material for supplying the electrical conductivity controlling substance are as follows. To supply atoms of group III, in particular boron atoms, boron hydrides, such as BpHg, BJLq, B ₅ H ₉ , BgH ^ ,, BgH.Q, BgH ", BgH ₁₄ , and boron halides, such as BF ₃ , BCl , and BBr ₃ , serve. Materials such as AlCl ₃ , GaCl ₃₅ Ga (CH ₃ J ₃ , InCl ₃ and TlCl ₃ are useful for introducing other Group III atoms.

For the supply of atoms of group V, in particular phosphorus, phosphorus hydrides, such as PH ₃ and P ₂ H ₄ , and phosphorus halides, such as PH ₄ J, PF ₃ , PF ₅₅ PCl ₃₅ PCl ₅ , PBr ₃ , PBr, - and PJ ₃ suitable. Materials such as AsH ₃ , ^ ?, AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃₅ SbF ₅ , SbCl ₃₅ SbCl ₅₅ BiH ₃ , BiCl ₃ and BiBr ₃ are suitable for introducing other Group V atoms.

These materials can be used alone or in combination with one another.

In the method of forming the heat generating resistor film described above, the amounts of the in the to be formed Resistance film 14 contained silicon atoms, germanium atoms, halogen atoms, Hydrogen atoms and the electrical conductivity-controlling substance as well as the properties of the resistance film 14 by suitable selection of factors such as the substrate temperature, Feed rates of gas materials, electrical Discharge power and pressure in the deposition chamber can be controlled.

If you get a heat generating resistance film 14 wants, in which at least one component of the Si atoms, germanium atoms, Halogen atoms, hydrogen atoms and the substance controlling electrical conductivity have an uneven distribution in In the direction of the thickness, the speed or speeds of introduction are preferably varied at least

one of the silicon atoms, germanium atoms, halogen atoms, hydrogen atoms and the electrical conductivity controlling substance over time by means of a control valve or another suitable means.

The Substrattenperatur is preferably selected in the range from 20 to 1500 ⁰ C, in the preferred cases from 30 to 1200 ⁰ C and in particular zwisehne 50 and 1100 ⁰ C.

The feed rate of the gas material becomes appropriate is selected in consideration of the heat generating property of the film and the film forming speed.

The electrical discharge power is preferably in the range between 0.001 and 20 W / cm ² , in the more preferred cases between 0.01 and 15 W / cm ² and in particular between 0.05 and 10 W / cm ² .

Finally, there is pressure in the separation chamber.

-4 preferably in the range between 10 and 10 Torr, in particular

_2
between 10 and 5 torr.

The one made by the method described above Resistance film of the recording head of the invention has properties similar to diamond. For example, the Vickers hardness of this film in the range of 1800 to 5000. The formation of the heat-generating resistance film is through facilitates the insertion of the halogen atoms and hydrogen atoms. At the same time, you get superior mechanical properties if Silicon atoms are included. It should also be noted that the Flexibility of the heat generating resistor film by the addition of germanium atoms to the a-C: (X, H) type material is improved.

The heat generating resistive film used in the recording head of the invention does not require a protective layer on the film as it has a long durability over mechanical Bump and shows high resistance. Therefore, the liquid jet recording head including this heat generating resistive film allows the invention has a high performance of heat transfer to the recording liquid due to the input signal, so that a high thermal response characteristic is achieved. This, in turn, improves the flying properties of the droplets due to those supplied to the recording head Signals.

However, the invention does not exclude a protective layer on the heat generating resistive film provided that the protective layer does not significantly affect the response. In fact, the protective layer is essential if the recording liquid is electrically conductively _s so that any short-circuit of the electric current between the two electrodes avoided by the liquid.

In the electricity / heat conversion element described above the heat generating resistor film is formed on the substrate and occupied by the electrodes. However, this is not the case essential, and the arrangement can also be such that the electrodes are sandwiched between the substrate and the heat generating Resistance film are inserted. Figure 4 shows a modified embodiment in which the electrodes 16 and 17 directly on the Substrate 12 is formed and covered with the heat generating resistor film 14.

Although the substrate 12 has been illustrated as being comprised of a single body, the substrate used in the invention may be a composite body. Figure 5 shows an example of such a composite substrate. This substrate accordingly has a base part 12a and one on the base part 12a

formed surface layer 12b.

The base part 12a can consist of the same material as the substrate material explained with reference to FIGS. 1 to 3, while the surface layer 12b is formed from one material which shows a higher affinity for the resistive film 14 to be formed thereon. Thus, the surface layer 12b can be made of an amorphous material having a matrix of carbon atoms or a suitable known oxide. The surface layer 12b can be used in the same way as in the above-explained formation of the heat-generating resistance layer by deposition be formed on the base part 12a of a suitable material.

The surface layer 12b can be a glazing layer made of an ordinary glass or - if the base part is made of a metal consists - be an oxide layer, which is formed by oxidation of the surface of such a metal base part.

The electrodes 16 and 17 can be made of any known material having the required conductivity, e.g. Metals such as Au, Cu, Al, Ag and Ni.

The recording head of the invention can be manufactured by the following method using an apparatus which shown by way of example in FIG. 6 and the formation of the heat-generating resistor film by deposition on the substrate surface is adapted.

Referring to Figure 6, the apparatus for forming the heat generating resistor film has the following components: a deposition chamber 1101; Gas cylinders 1102 to 1106; Mass flow controller 1107 to 1111; Intake valves 1112 to 1116; Exhaust valves 1117 to 1121; Gas cylinder valves 1122 through 1126; Outlet pressure gauge 1127 to 1131; an auxiliary valve 1132; a lever 1133;

a main valve 1134; a leak valve 1135, a vacuum gauge 1136; a substrate 1137 on which the heat generating resistor film is to be formed; a heater 1138; a substrate holder 1139; a high voltage electric supply unit 1140; an electrode 1141; and a shutter 1142. Numeral 1142-1 denotes a target that can be attached to the electrode 1141 when the atomization is to be carried out.

To form a heat generating resistor film from aC: (X, H), the procedure is as follows. The gas cylinder 1102 is _{filled with CF 4} gas (99.9% or higher purity) diluted with Ar gas, while the gas cylinder 1103 is filled with CJ 4 gas (99.9% or higher purity) that is is also diluted with Ar gas. On the other hand, the gas cylinder 1104 is _{filled with H 2} -GaS (99.9 % or higher purity), while the gas cylinder 1105 is filled with CHF ₃ -GaS (99.9 % or higher purity) which is Ar gas is diluted. Before allowing the gases from these bottles to flow into the separation chamber 1101, the operator makes sure that the valves 1122 to 1126 of all gas bottles 1102 to 1106 are closed and that the inlet valves 1112 to 1116, the outlet valves 1117 to 1121 and the auxiliary valve 1132 are open. The operator then opens the main valve 1134 to evacuate the deposition chamber 1101 and the associated gas lines. When the display of the vacuum gauge 1136 has reached the value 1.5 x 10 ~ Torr, it closes the auxiliary valve 1132, the inlet valves 1112 to 1116 and the outlet valves 1117 to 1121. Then the valves of the gas bottles with the gases to be used are opened so that these gases are introduced into the deposition chamber 1101.

When the above-mentioned resistive film with this apparatus is formed by glow discharge, the procedure is as follows.

First, valve 1122 is opened _{to dispense the CF 4} Mr GaS from gas cylinder 1102, and valve 1124 is opened.

net to discharge the hL gas from the gas cylinder 1104 while regulating the pressure indicated by the outlet pressure gauges 1127 and 1129 to 1 kg / cm ² . Thereafter, the inlet valves 1112 and 1114 are gradually opened to allow the gases to flow into the mass flow regulators 1107 and 1109. Then, the exhaust valves 1117, 1119 and the auxiliary valve 1132 are gradually opened to introduce the CF./Ar gas and the hL gas into the deposition chamber 1101. In the meantime, the operator sets the mass flow controllers 1107, 1109 to a desired ratio of the flow rates of the CF./Ar gas and H ₂ gas; Likewise, he adjusts the opening of the main valve 1134, taking into account the indication of the vacuum gauge 1136, so that a desired pressure is maintained in the deposition chamber 1101. After the heater 1138 is turned on to heat the substrate 1137 on the holder 1139 to a desired temperature, the shutter 1142 is opened to start the glow discharge in the deposition chamber 1101.

To form an uneven distribution of halogen atoms and / or hydrogen atoms in the thickness of the resistor film from a-C: (X, H), the 'opening of the exhaust valve 1117 and / or the opening of the outlet valve 1119 is varied by hand or by an external drive motor in such a way that the flow velocities of the CF./Ar gas and / or the H "gas over time change along a predetermined rate of change curve, whereby a change in the content of the F atoms and / or H atoms in the thickness of the product film 14 is achieved.

When the above-mentioned resistor film with the explained Apparatus formed by the atomization method, the method is as follows.

A piece of graphite 1142-1 of high purity is first placed as a target on electrode 1141, to which an electrical High voltage supply unit 1140 a high voltage

can be created. Then the CHF-j / Ar gas comes out of the bottle 1105 into the deposition chamber at a desired flow rate 1101, as is the case with film formation by glow discharge. Then the shutter 1142 is opened, and the power supply unit 1140 is turned on, whereby sputtering takes place on the target 1142-1. In the meantime the substrate 1137 is heated to the desired temperature by the heater 1138 and kept at this temperature, and the opening of the Master valve 1134 is set to the desired deposition chamber pressure as in glow discharge film formation.

In the formation of the heat generating resistor film a-C: (X, H) by atomization can cause an uneven distribution of halogen atoms and / or hydrogen atoms in the direction of the Thickness can be achieved in the same way as film formation by glow discharge. For this purpose, the 'opening of the Exhaust valve 1120 varies in the same manner as in the glow discharge, so that the flow rate of the CHF, / Ar gas varies with time along a predetermined rate of change curve and thus a change in the content of F atoms and / or the Η atoms in the thickness of the resistor film 14 is achieved.

To form a heat generating resistor film of aC: Si: (X, H) using the system shown in Figure 6, the process can be as follows. The gas cylinder 1102 is _{filled with CF 4} gas (99.9 % or higher purity) diluted with Ar gas. The gas cylinder 1103 is _{filled with C 2} F ₅ gas (99.9 % or higher purity), which is also diluted with Ar gas. On the other hand, the gas cylinder 1104 is filled with SiH "gas (99.9% or higher purity) diluted with Ar gas, while the gas cylinder 1105 is filled with Si ₂ H ₆ gas (99.9 % or higher Purity) diluted with Ar gas. Then, the valves of the respective bottles with the gases to be introduced into the deposition chamber 1101 were opened to release them

Introduce gases as in the formation of the resistive film of the composition aC: (X ₅ H).

When the above-mentioned heat generating resistor film _{having the composition aC: Si; (X 5} H) is formed by glow discharge with this apparatus, the procedure can be as follows.

First, the valve 1122 is opened _{to discharge the CF 4} Mr GaS from the gas cylinder 1102, and the valve 1124 is opened to discharge the SiH ^ / Ar gas from the gas cylinder 1104 during that indicated by the outlet pressure gauges 1127 and 1129 Pressure is regulated to 1 kg / cm ^2. Then the inlet valves 1112 and 1114 are gradually opened to allow the gases to flow into the mass flow regulators 1107 and 1109. Then, the exhaust valves 1117, 1119 and the auxiliary valve 1132 are gradually opened to introduce the CF 1 / Ar gas and the SiH ₄ gas into the deposition chamber 1101. Meanwhile, the operator sets the mass flow controllers 1107 and 1109 to a desired ratio of the flow rates of the CF »/ Ar gas and SiH. Gas; likewise, he adjusts the opening of the main valve 1134 in accordance with the indication of the vacuum gauge 1136 so that a desired pressure is maintained in the deposition chamber 1101. After the heater 1138 is turned on to heat the substrate 1137 on the holder 1139 to a desired temperature, the shutter 1142 is opened to start the glow discharge in the deposition chamber 1101.

To achieve a non-uniform distribution of the silicon atoms, halogen atoms and hydrogen atoms in the resistance film made of aC: Si: (X, H), the opening of the outlet valve 1117 and / or the opening of the outlet valve 1119 are varied by hand or by an external drive motor so that the flow rates of the CF ₄ / Ar gas and / or the SiH ₄ / Ar gas change with time along a predetermined rate of change curve, whereby a change in the content at least

3518596

one of Si atoms, F atoms and Η atoms in the product film 14 is achieved.

When the above-mentioned resistor film with the explained Apparatus formed by the atomization method, the method is as follows.

A piece of graphite 1142-1 of high purity is first placed as a target on electrode 1141, to which an electrical High-voltage supply unit 1140, a high voltage can be applied. Then the CF "/ Ar gas and the SiH" / Ar gas similar to the case of film formation by glow discharge at the respective desired flow rates into the deposition chamber Introduced in 1101. Then the shutter 1142 is opened and the power supply unit 1140 is switched on, whereby sputtering occurs on target 1142-1. Meanwhile, the substrate 1137 is heated by the heater 1138 to the desired Temperature heated and held at this, and the opening of the main valve 1134 is as in the film formation by glow discharge adjusted to the desired pressure of the deposition chamber.

When the aC: Si: (X ₅ H) heat generating resistor film is formed by sputtering, uneven distribution of at least one of silicon atoms, halogen atoms and hydrogen atoms can be achieved in the thickness direction in the same manner as in the film formation by glow discharge. For this purpose, namely, the opening of the outlet valve 1117 and / or 1119 is varied in the same way as in the glow discharge, so that the flow rate of the CF ₄ / Ar gas and / or that of the SiH2 / Ar gas over time along a predetermined amount Finding speed curve varies and so a change in the content of at least one of Si atoms, F atoms and Η atoms in the direction of the thickness of the resistor film 14 is achieved.

To form a heat generating resistive film of aC: Ge: (X, H) using the system shown in Figure 6, the procedure can be as follows. Gas bottle 1102 is filled with CF. gas (99.9% or higher purity) which is diluted with Ar gas. The gas cylinder 1103 is filled with GeH. Gas (99.9 % or higher purity) which is diluted with Ar gas. On the other hand, the gas cylinder 1104 is filled with C ^ Fg gas (99.9% purity or higher) diluted with Ar gas. Then, the valves of the respective bottles with the gases to be introduced into the deposition chamber 1101 are opened to introduce these gases as in the formation of the resistance film of the composition aC: (X, H).

When the above-mentioned heat generating resistor film _{having the composition aC-Ge: (X 5} H) is formed with the apparatus by glow discharge, the procedure can be as follows.

First, the valve 1122 is opened to release the CF./Ar gas from the gas cylinder 1102 and the valve 1124 is opened to release the GeH./Ar gas from the gas cylinder 1104 during that through the outlet gauges 1127 and 1129 indicated pressure is regulated to 1 kg / cm ^2. Thereafter, the inlet valves 1112 and 1114 are gradually opened to allow the gases to flow into the mass flow regulators 1107 and 1108. Then, the exhaust valves 1117, 1118 and the auxiliary valve 1132 are gradually opened to introduce the CF./Ar gas and the GeH ^ / Ar gas into the deposition chamber 1101. Meanwhile, the operator adjusts the mass flow controllers 1107 and 1108 to a desired ratio of the flow rates of the CF./Ar gas and the GeH2 / Ar gas, and also adjusts the opening of the main valve 1134 in accordance with the indication of the vacuum gauge 1136 that a desired pressure is maintained in the deposition chamber 1101. After the heater 1138 has been switched on for the purpose of heating the substrate 1137 located on the holder 1139 to a desired temperature, the shutter 1142 is opened to the

Start glow discharge in the deposition chamber 1101.

To achieve an uneven distribution of at least one of the germanium atoms, halogen atoms and hydrogen atoms in the resistance film made of aC: Ge: (X ₅ H), the opening of the outlet valve 1117 and / or the opening of the outlet valve 1119 are varied by hand or by an external drive motor, that the flow rates of the CF./Ar gas and / or the GeH./Ar gas change with time along a predetermined rate of change curve, whereby a change in the content of at least one of the Ge atoms, F atoms and Η atoms in the product film 14 is reached.

When the above-mentioned resistor film by sputtering is formed with the above-mentioned apparatus, the procedure is as follows.

A piece of graphite 1142-1 of high purity is first placed as a target on the electrode 1141, to which a high voltage can be applied by a high-voltage electrical supply unit 1140. Then the CF./Ar gas and the GeH ₄ Mr gas are introduced into the deposition chamber 1101 from the bottles 1102 and 1103 at the respective desired flow rates, as in the case of film formation by gas discharge. Then, the shutter 1142 is opened and the power supply unit 1140 is turned on, thereby sputtering on the target 1142-1. In the meantime, the substrate 1137 is heated to and maintained at the desired temperature by the heater 1138, and the opening of the main valve 1134 is set to the desired pressure of the deposition chamber as in the case of film formation by glow discharge.

In the formation of the heat generating resistor film of aC: Ge: (X ₅ H) by sputtering, uneven distribution of at least one of germanium atoms, halogen atoms and hydrogen atoms in the thickness direction may be caused in the same manner as in

the film formation can be achieved by glow discharge. For this purpose, the opening of the outlet valve 1117 and / or 1118 in the varies in the same way as the glow discharge, so that the flow rate of the CF ^ / Ar gas and / or that of the GeH./Ar gas over time along a predetermined rate of change curve varies and so a change in the content of at least one of the Ge atoms, F atoms and Η atoms in the direction the thickness of the resistive film is achieved.

To form a heat generating resistor film of aC: Si: Ge: (X ₅ H) using the system shown in Figure 6, the process can be as follows. The gas cylinder 1102 is _{filled with CH 4} -GaS (99.9 % or higher purity) diluted with Ar gas, while the gas cylinder 1103 _{is filled with SiH 4} -GaS (99.9 % or higher purity) which is is diluted with Ar gas. On the other hand, the gas cylinder 1104 is filled with GeF ₄ -GaS (99.9 % or higher purity) diluted with Ar gas, while the gas cylinder 1105 is filled with SiF ₄ -GaS (99.9 % or higher purity) which is diluted with Ar gas. Finally, the gas cylinder 1106 is filled with GeH ₄ gas (99.9 % or higher purity) diluted with Ar gas. Then, the valves of the respective bottles with the gases to be introduced into the deposition chamber 1101 are opened to introduce these gases as in the formation of the resistance film of the composition aC: (X, H).

When the above-mentioned heat generating resistance film the composition a-C: Si: Ge: (X, H) is formed with the apparatus by glow discharge, the process can proceed as follows.

First, the valve 1122 is opened to discharge the CH./Ar gas from the gas cylinder 1102, and the valve 1123 is opened to discharge the SiH ₄ Mr GaS from the gas cylinder 1103, and the valve 1124 is also opened to to discharge the GeF ₄ / Ar gas from the gas cylinder 1104 while regulating the pressure indicated by the outlet pressure gauges 1127, 1128 and 1129 to 1 kg / cm ² .

Thereafter, the intake valves 1113 and 1114 gradually become opened to allow gases to flow into mass flow controllers 1107, 1108 and 1109. Then the exhaust valves 1117, 1118 and 1119 and also the auxiliary valve 1132 gradually opened to let the CH./Ar gas, Si H./Ar gas and GeF./Ar gas into the deposition chamber 1101 to be introduced. In the meantime the operator sets the mass flow controller 1107, 1108 and 1109 to a desired ratio of the flow rates of the Cf-L / Ar gas, SihL / Ar gas and GeF./Ar- gases a; he also sets the "opening of the main valve" 1134, observing the indication of the vacuum gauge 1136, so that a desired pressure is maintained in the deposition chamber 1101 will. After the heater 1138 has been switched on for the purpose of heating the substrate 1137 located on the holder 1139 At a desired temperature, the shutter 1142 is opened to start the glow discharge in the deposition chamber 1101.

In order to achieve an uneven distribution of at least one of the germanium atoms, silicon atoms, halogen atoms and hydrogen atoms in the resistance film made of aC: Si: Ge: (X ₅ H), the opening of at least one of the outlet valves 1117, 1118 and 1119 is done by hand or by an external drive motor varies so that the flow rate of at least one of the CH ^ / Ar gas, SiH »/ Ar gas and GeF./Ar gas changes with time along a predetermined rate of change curve, whereby a change in the content of at least one of the Si atoms, Ge atoms, F atoms and Η atoms in the product film is achieved.

When the above-mentioned resistor film by sputtering is formed with the above-mentioned apparatus, the procedure is as follows.

A piece of graphite 1142-1 of high purity is first placed as a target on electrode 1141, to which an electrical High voltage supply unit 1140 a high voltage can be created. Then the CH./Ar- gas, the SiH./Ar- gas

and the GeF./Ar gas similar to film formation by glow discharge with the respective desired flow rates from the gas bottles 1102, 1103 and 1104 into the deposition chamber Introduced in 1101. Then the shutter is opened and the power supply unit 1140 is switched on, whereby the Target 1142-1 sputtering takes place. Meanwhile, the substrate 1137 is heated to the desired temperature by the heater 1138 heated and held on this, and the opening of the main valve 1134 is as in the film formation by glow discharge to the desired Deposition chamber pressure set.

In the formation of the heat generating resistance film of aC: Si: Ge: (X ₅ H) by sputtering, uneven distribution of at least some of the silicon atoms, germanium atoms, halogen atoms and hydrogen atoms in the direction of thickness can be achieved in the same manner as in the film formation by glow discharge . For this purpose, the opening of at least one of the outlet valves 1117, 1118 and 1119 is varied in the same way as with the glow discharge, so that the flow rate of at least one of the CH »/ Ar, SiH./Ar and GeF./Ar gases is also varied varies with time along a predetermined rate of change curve and thus a change in the content of at least one of Si atoms, Ge atoms, F atoms and Η atoms in the direction of the thickness of the resistor film is achieved.

Examples of methods of forming a heat generating resistor film from a-C: (X, H) (p, n) representing the heat generating one Resistance films with an electrical conductivity controlling substance are explained below. However, it is Note that the procedures outlined below apply equally to other types of material with an electrical Conductivity-controlling substance are applicable, namely to aC: Si: (X, H) (p, n), aC: Ge: (X, H) (p, n) and aC: Si: Ge: (X, H) (p, n), which one goes through Introduction of electrical conductivity controls Substance in the aforementioned materials of the cons

standsfiims, namely a-C: Si: (X, H), a-C: Ge: (X, H) and a-C: Si: Ge: (X, H) receives. The procedures for these materials are therefore not given in the description.

When the heat generating resistor film of the composition a-C: (X, H) (p, n) using the system shown in FIG is produced, the procedure is basically as follows.

The gas cylinder 1102 is filled with CF ^ gas (99 ₅ 9 % or higher purity) which is diluted with Ar gas, while the gas cylinder 1103 _{is filled with PH 3} gas (99.9 % or higher purity) which is is diluted with Ar gas. Likewise, the bottle 1104 is _{filled with B 2} Hg-GaS (99.9 % or higher purity) diluted with Ar gas. Before allowing the gases from these cylinders to flow into the separation chamber 1101, the operator assures that the valves 1122 through 1126 of all gas cylinders 1102 through 1106 are closed and that the inlet valves 1112 through 1116, the outlet valves 1117 through 1121 and the auxiliary valve 1132 are open . The operator then opens the main valve 1134 to evacuate the deposition chamber 1101 and the associated gas lines. When the display of the vacuum gauge 1136 has reached the value 1.5 x 10 ~ ⁶ Torr, it closes the auxiliary valve 1132, the inlet valves 1112 to 1116 and the outlet valves 1117 to 1121. Then the valves of the gas bottles with the gases to be used are opened, see above that these gases are introduced into the deposition chamber 1101.

When the resistive film of a-C: (X, H) (p, n) is formed by glow discharge with this apparatus, the method is as follows.

First, the valve 1122 is opened to supply the CF, / Ar gas to dispense from the gas bottle 1102, and the valve 1123 is opened to dispense the PH ~ / Ar gas from the gas bottle 1103, while that indicated by outlet pressure gauges 1127 and 1128

Pressure is regulated to 1 kg / cm ^2. Thereafter, the inlet valves 1112 and 1113 are gradually opened to allow the gases to flow into the mass flow regulators 1107 and 1108. Then, the exhaust valves 1117, 1118 and the auxiliary valve 1132 are gradually opened to introduce the CF./Ar gas and the PH_ / Ar gas into the deposition chamber 1101. Meanwhile, the operator adjusts the mass flow controllers 1107 and 1108 to a desired ratio of the flow rates of the CF »/ Ar gas and the PH ^ / Ar gas; likewise, he adjusts the opening of the main valve 1134 in accordance with the indication of the vacuum gauge 1136 so that a desired pressure is maintained in the deposition chamber 1101. After the heater 1138 is turned on to heat the substrate 1137 on the holder 1139 to a desired temperature, the shutter 1142 is opened and the glow discharge in the deposition chamber 1101 is started.

To achieve a non-uniform distribution of at least one of the halogen atoms, hydrogen atoms and the electrical Conductivity controlling substance in the resistive film from a-C: (X, H) (p, n) the opening of the outlet valve 1117 and / or of the outlet valve 1118 is made manually or by an external one Drive motor varies so that that of the CF »/ Ar gas and / or the ΡΗ -, / Ar gas along a predetermined rate of change curve with time changes, causing a change in the content of at least one of the F atoms, Η atoms and the electrical Conductivity controlling substance in the product film 14 · achieved will.

When the above-mentioned resistance film of a-C: (X, H) (p, n) is formed with the above-mentioned apparatus by sputtering the procedure can be as follows.

A piece of graphite 1142-1 of high purity is first placed as a target on the electrode 1141, to which a high voltage can be applied by a high-voltage electrical supply unit 1140. Then the CF ^ / Ar gas and the PH _{3 become} Mr GaS

as in the case of glow discharge film formation with the desired Flow rates from bottles 1102 and 1103 introduced into separation chamber 1101. Then the shutter 1142 is opened and the power supply unit 1140 is switched on, as a result of which sputtering takes place on the target 1142-1. In the meantime the substrate is heated to the desired temperature by the heater 1138 and kept at this temperature, and the opening of the main valve 1134 is adjusted to the desired pressure in the deposition chamber as in film formation by glow discharge.

In order to achieve a non-uniform distribution of at least one of the halogen atoms, hydrogen atoms and the substance controlling the electrical conductivity in the _{resistive film consisting of aC: (X 5} H) (p, n), the opening of the outlet valve 1117 and / or the outlet valve 1118 is varied, to change the flow rate of the CF ^ / Ar gas and / or the PH ₃ / Ar gas over time along predetermined rate of change curves and so the content of at least one of the F atoms and H atoms and the electrical conductivity-controlling substance as in the Change film formation by glow discharge in the direction of thickness.

The electrothermal conversion element of the type shown in Figures 1 to 3 for use in the liquid jet recording head of the invention is made by forming the heat-generating resistive film on the substrate in the manner described above, conductive layers on the heat-generating resistive film, for example, an Au layer and an Al layer, as electrodes, and pattern formation of the conductive layers and the heat-generating resistor film is carried out by known photolithographic methods. If necessary, a protective layer covering the heat generating resistor film and the electrodes is formed.

On the other hand, it becomes the electricity / heat converting element of the type shown in Figure 4 for use in the liquid jet recording head of the invention is formed by; that you first have a conductive layer on the substrate forms a pattern by a photolithographic technique the conductive layer and the heat-generating resistor film by glow discharge or sputtering as explained above forms.

The cover plate of the recording head is made of a similar material as the substrate. The channels are through a suitable process, such as mechanical milling using a micro-milling cutter, chemical etching, etc. If a light-sensitive Glass is used as the material, the channels can be formed by exposure in the desired pattern and subsequent development will.

The connection of the cover plate to the substrate is carried out by bonding with an adhesive, after a sufficient positional Alignment is done. Some types of material for the cover plate allow the cover plate to be connected to the substrate to be achieved by fusion welding.

In the embodiment of the liquid jet recording head described here the outlet 26 of the recording liquid is formed at one end of the channel 22 which is the liquid passage limited in the cover plate 20, as is shown for the typical case in FIG. This location of the outlet however, the recording liquid does not exclude other layers, and the outlet 26 for the recording liquid may also be formed on the top of the cover plate 20, as shown in FIG. In this case, the end openings can be a each channel defining the liquid passage as a recording liquid inlet serve through which the recording liquid is introduced into the liquid passage, and the

Recording liquid is ejected as a jet through the exit 26 as shown by arrow Y. In this case each channel can of course be closed at one end so that the liquid can flow through the open end of each channel is introduced.

A modification of the liquid jet recording head of the described embodiment will be explained below.

According to FIG. 9, which is a section along the line IX-IX of FIG. 8, the cover plate 20, if not the channels exist with the substrate of the electrothermal conversion element kept in contact. Therefore, the sections 24 formed along the channels 22 in question are through the Strips 30 isolated from one another, which by the contacting the substrate Sections of the cover plate 20 are formed. In the arrangement shown in Figure 9, the heat-generating zones 18 are in the relevant channels near the outputs 26 is provided.

Figs. 10 and 12 are sections of various examples of the recording head of the described embodiment according to FIG Line IX-IX of FIG. 8.

In the recording head shown in Figure 10, the lands 30 do not contact the substrate 12, so that the heat generating Zones 18 corresponding heating sections 24 are in communication with one another. That is, the liquid passages are not independently as shown in Figure 9, but adjacent liquid passages are in communication with each other.

In the recording head shown in Figure 11, the ridges 30 are not in the cover plate 20 but in the substrate educated. Therefore, the heating sections 24 communicate with each other as in the recording device shown in FIG.

head is the case. Therefore, in this case too, adjacent liquid passages are in communication with one another.

The recording head shown in Fig. 12, unlike the recording heads of Figs. 10 and 11, does not have a land. In this In this case, therefore, the liquid passage is formed by an ink chamber which is common to all heating sections 24.

The various examples shown in Figs. 9 to 12 which are modifications of the recording head shown in Fig. 8 can also be applied to the liquid jet recording head realize the type shown in Figure 7.

The presence of the webs 30 is not essential. the Bridges can namely also be omitted, provided that the range and the target of the flying droplets are a predetermined Do not leave the tolerance range, although it is true that the direction, speed and strength of the liquid jet by standing in the adjacent liquid outlets Fluid are affected. The formation of webs is preferred, however, in order to avoid mutual influences between neighboring Reduce fluid outflows and improve energy conversion efficiency. It is clear to the person skilled in the art that the webs can be formed in one piece with the cover plate or can be formed as independent bodies, which are then conveniently attached to the cover plate. the Flat cover plate can be made of the same material as the cover plate discussed above with channels. Hardened Films made of a photosensitive resin can be used as the material of the webs and the cover plate serve.

From the foregoing description, it can be seen that the present invention is a liquid jet recording head with built-in electricity / heat conversion element with a heat generating resistor film made of a halogen atom and Hydrogen atoms contained in a matrix of carbon atoms

creates amorphous material as well as a liquid jet recording system, in which this recording head is built. The heat generating resistor film made of the above amorphous material shows high chemical resistance, excellent resistance to electrochemical reactions and oxidation as well as excellent resistance to mechanical shock and heat. Accordingly, the liquid jet recording head has and the system according to the invention has various excellent properties, particularly high thermal response and durability with repeated use. Further, the invention allows the heat generating resistor film to be easily formed. As a result, the present invention provides a liquid jet recording head having high reliability and high frequency responsiveness realized. Furthermore, the use of the amorphous material containing silicon atoms ensures high mechanical properties Strength of the electricity / heat converting element while the incorporation of germanium atoms into the amorphous material gives excellent flexibility of the heat generating resistor film. When contain silicon atoms and germanium atoms at the same time resistance to chemicals and flexibility are advantageously improved. If, in addition, the electrical Conductivity-controlling substance is contained, the Controllability of the resistance of the heat generating resistor film improved.

Furthermore, there is at least one component among silicon atoms, germanium atoms, halogen atoms, hydrogen atoms and the substance that controls electrical conductivity may have uneven distribution in the direction of the thickness of the heat generating resistor film can easily be different Realize desired properties, such as heat accumulation capacity, Thermal radiation, affinity between substrate and resistive film and resistance to chemical reaction.

Practical examples of the liquid jet recording head according to the invention are described below.

Examples:

Examples (Nos. P-I to P-56, S-I to S-6) of the series of Electric / heat converting elements for use in the liquid jet recording head of the invention and a comparative example were carried out according to the following procedures.

No. 7059 glass manufactured by Corning Glass Works was used as the substrate material. A surface layer of thermally oxidized SiOp in a thickness of 5 μm was formed as a heat accumulation layer. In each case were on the substrate a heat generating resistance layer and electrodes were formed, and a protective layer was formed if necessary. the Layer structures of the heat generating resistor film, electrodes and protective layer were made in the following three types A, B and C manufactured.

The heat generating resistor film was formed on the substrate by the deposition system discussed above in connection with FIG. The conditions of the deposition were given in Tables 1, 2, 4, 5, 7, 8, 10, 12, 14, 16, 20 and 22. The examples in Tables 1, 4, 7, 10, 12, 14, 16, 18, 20 and 22 were produced by glow discharge, while the examples shown in Tables 2, 5 and 8 and the comparative example were produced by sputtering. In the sputtering for the production of the examples given in Tables 2 and 5, graphite (99.9 % purity) served as the target material, while the sputtering when carrying out the comparative _{example HfB?} used as target material.

The comparative example carried out under the same conditions was used for comparison in a first case (a-C: (X, H)),

a second case (aC: (X ₅ H) with uneven distribution of the X atoms and / or the Η atoms), a third case (aC: Si: (X ₅ H)), a fourth case (aC :: Si : (X ₅ H) with uneven distribution of at least one component among the Si atoms, X atoms and Η atoms), a fifth case (aC: Ge: (X, H)) ₉ a sixth case (aC: Ge: (X ₅ H) with uneven distribution of at least one component among the Ge atoms, X atoms and H atoms), a seventh case (aC: Si: Ge: (X, H)) ₅ an eighth case (aC: Si : Ge: (X ₅ H) with uneven distribution of at least one component among Si atoms, Ge atoms, X atoms and H atoms) and in other cases where the electrical conductivity controlling substance is the respective above-mentioned amorphous Compositions is added.

During the deposition, the gas flow rates and other conditions as shown in Tables I ₅ 2, 4, 5, 7, 8, 10, 12, 14, 18, 20 and 22 were maintained so that heat-generating resistance films with the properties shown in Tables 3 , 6, 9, 11, 13, 15, 17, 19, 21 and 23 specified thicknesses were formed.

Then it was after on the heat generating resistor film the electron beam process an Al layer formed, and through A resist pattern was formed using the photolithographic technique. Using this resist pattern, the Al layer was etched, so that several pairs of electrodes were formed. Then another resist pattern was formed by photolithographic technique, and became unnecessary parts of the heat generating resistance film removed by etching with a cooling liquid of the HF system. Accordingly, a plurality of heat generating resistance elements were formed, each of which constitutes a heat generating zone from a part of the heat-generating resistance film of 40 μπι χ 200 pm and on it had deposited electrodes. The density of the heat generating zone was 8 per millimeter.

A layer of photosensitive polyimide (trade name Photoneece) was then formed by spin coating. After a 1-hour pre-cure at 80 ⁰ C, the heat generating element was exposed an aligner using and then developed, so as to form an opening or a window in each of the heat generating zone. Finally, the heat generating element was post-cured for 30 minutes at 140 ⁰ C and 1 hour at 400 ⁰ C, whereby the series of electrical / thermal converting elements has been completed.

The resistance values of the heat generating zones in the various The electricity-to-heat conversion elements produced by the method described above are shown in Tables 3, 6, 9, 11, 13, 15, 17, 19, 21, and 23 indicated. The photosensitive polyimide was used to prevent any electrolysis of the Al electrode in the Prevent ink.

The thus completed series of electricity / Heat conversion elements is in schematic perspective View in Figure 13 and shown in a schematic cross-sectional view in Figure 14. In these figures, reference numeral 28 denotes a polyimide layer.

A heat-generating resistive film could be on anyone Substrate in the same manner as for Type A among those given in Tables 1, 2, 4, 5, 7, 8, 10, 12, 14, 16, 18, 20 and 22 Deposition conditions are formed. During the deposition, the gas flow rates and other factors were taken into account according to the information in tables 1, 2, 4, 5, 7, 8, 10, 12,

14, 16, 18, 20 and 22 are observed, so that the heat-generating resistor films in the various in Tables 3, 6, 9, 11, 13,

15, 17, 19, 21 and 23 specified thicknesses were formed. Then was on the heat generating resistor film by the electrons Beam method formed an Au layer and it was through

A resist pattern was formed using a photolithographic technique. Under Using this resist pattern, the Au layer was etched to form a plurality of pairs of electrodes. Then was done by photolithographic Technique, another resist pattern was formed, and the unnecessary parts of the heat generating resistor film were made Etched away with a sticky liquid from the HF system. Accordingly was a plurality of heat-generating resistance elements are formed, each of which constitutes a one-part heat-generating zone of the heat generating resistor film in the size of 40 pm χ 200 µm and electrodes deposited thereon. The density of heat generating zones was 8 per millimeter. The resistance values of the heat generating zones in the different, by the above described method produced electricity / heat conversion elements are as given in the case of type A in Tables 3, 6, 9, 11, 13, 15, 17, 19, 21 and 23. The construction of the thus completed A row of electricity-to-heat conversion elements is shown in the schematic perspective view in FIGS shown in the schematic section in FIG.

On the substrate was made by the electron beam method an Al layer is formed on which by photolithographic Technique a resist pattern was formed. Using this resist pattern, a plurality of pairs of electrodes were formed on the Al layer educated. Then a heat generator became on the Al layer Resistance film is formed. This was done using the same procedure as for type A. The deposition conditions were adhered to in such a way that as shown in Tables 1, 2, 4, 5, 7, 8, 10, 12, 14, 16, 18, 20 and 22, so that the heat generating resistive film were formed in various thicknesses according to the information in Tables 3, 6, 8 and 10. Then another resist pattern became formed by photolithographic technique, and the unnecessary part of the heat generating resistor film was removed by an etching liquid of the HF system. Accordingly, they became heat generating Resistance elements are formed, each of which is one

- Oo -

heat-generating zone from part of the heat-generating resistive film in the size of 40 μπι χ 200 μπι and deposited thereon Had electrodes. The density of the heat-generating zones was 8 per millimeter. In this case, the Al electrodes were through the heat-generating resistor film was effectively protected, so that it was not necessary to use a protective film for the electrodes to build. The resistance values of the heat generating zones of the electricity-to-heat conversion elements formed by the method described above are given as in the case of type A in Tables 3, 6, 9, 10, 11, 13, 15, 17, 19, 21 and 23. The structure of the series of electrothermal conversion elements thus formed is indicated in the schematic perspective illustration in FIG. 17 and in the schematic section in FIG.

Liquid jet recording heads have been used of the electrothermal conversion elements formed by the various methods described above. Broadly, two types of recording heads have been manufactured, namely Type I in the structure shown in Fig. 7 and Type II in the structure shown in FIG. The Type I recording head was manufactured by two different methods. The recording head manufactured by the first method is referred to as type 1-1, while that manufactured by the second method Method manufactured recording head is referred to as type 1-2.

The manufacturing processes were as follows.

Type 1-1

With reference to FIG. 19, a cover plate 20 with channels was formed from a glass plate 40. Multiple channels 22 that to form the liquid passages, each of which is 40 μπι wide and 40 μπι deep, and a groove 42, which has a common, to form the ink chamber communicating with the liquid passages were made by a micro-milling cutter in the glass plate 40 formed, whereby the cover equipped with channels

3S18596

plate 20 has been completed.

The cover plate 20 was then with each row in turn electricity-to-heat conversion elements formed by the methods described above connected in such a way that the heat generating zones in the electricity / heat conversion elements the channels 22 are aligned to form the liquid passages and the common ink chamber. Then were Ink inlet tubes 44 for introducing an ink into the common ink chamber connected to the kit, thereby forming an integral Recording head 46 was formed.

Type 1-2

Every electrothermal conversion element was coated with a photosensitive film 50 which is one of Tokyo Oka Kogyo film manufactured under the trade name Ordyl was. The coated element was then exposed through an aligner and developed so that the film 50 was a predetermined Pattern was formed. Then a glass plate 54, also with a photosensitive film 52 made of the same Material such as film 50 coated was adhered to the patterned film on the electrothermal transducer element. The so educated Body was then mechanically cut, such as by dicing, to expose the fluid outlets 26. then ink introduction tubes 44 were used for introducing an ink from a source (not shown) to the cut kit connected, thereby forming an integral recording head 56 as shown in the schematic perspective view FIG. 21 is shown.

Type II

As a first step in the manufacturing process, a cover plate 20 was formed which has liquid outlets 26 in its main surface. In particular, the cover plate 20 was made of a Stainless steel plate formed in which the channels, for example, through

Etching were formed. A sample of photosensitive film, that of Hitachi Chemical Go., Ltd. manufactured under the trade name PHT-145FT-50, was formed on the stainless steel plate, and a Ni plating layer was formed by an electroforming method educated. The liquid outlets 26 were formed in places where the photosensitive film pattern existed. The so The top plate 20 formed was adhered to the row of the electrothermal converting elements by an adhesive so that the heat-generating zones are aligned with the liquid outlets 26. The electricity / heat converting element was previously mechanically perforated in order to enable the ink to be fed into the common ink chamber in the cover plate 20. Then became a Ink introduction tube 60 for introducing an ink from a source (not shown) to the underside of the electrothermal transducer element connected, resulting in an integral recording head 62 as shown in the schematic perspective View of Figure 22 is shown. In FIG. 22, the number 64 designates recesses which are between the adjacent liquid outlets Create bridges. Thus, the type II recording head can have either the structure shown in Fig. 9 after the ridges are formed or have the structure shown in Figure 10 or even the in Structure shown in FIG. 12, which manages without webs.

So there are three types A, B and C in the in-line construction of the electrothermal conversion elements and three types 1-1, 1-2 and II of the recording head assembly, and are various combinations of these types possible.

Among these various combinations, a combination of the type A electrical / heat converting element and of the 1-1 type recording head assembly was subjected to a durability test described below with reference to those in Tables 3, 6, 9, 11, 13, 15, 17, 19, 21 and 23 are explained.

A lead board was attached to the recording head formed by the type A structure and the type 1-1 structure to complete the recording head unit. The lead board had electrode leads (not shown) which were connected to the corresponding heat-generating zones, independent electrodes 17 were connected, and an electrode lead (not shown) to the electrode 16, which was common to all heat generating zones.

Using this recording head unit, a liquid jet recording system shown in the schematic perspective view in FIG. 23 is assembled. As can be seen from this figure, this uses The liquid jet recording system comprises: the recording head unit 70; one is the recording head unit 70 carrying car 72; Guide body 72 for guiding the reciprocating movement of the carriage 72; and a roller 76. The number 78 denotes a recording medium held on the platen 76, such as a printing paper.

The recording head unit 70 is oriented so that the recording liquid outlets in the direction of arrow Z. are directed so that the droplets of the recording liquid can fly in the direction of arrow Z and in the form of dots deposited on the recording medium 78 located on the roller 76 will. The main scanning is performed by driving the recording head unit 70 by a suitable drive means along the guide body 74, while the auxiliary scanning is carried out so that the roller 76 is rotated by some other suitable drive means about the axis of the shaft 77, the information entered by which liquid points are recorded on the recording medium.

A test was made using this liquid jet recording system under the following conditions

guided.

Rectangular while impulses became the heat generating ones Zones fed. The pulse width was 10 µsec and the period was 200 psec. The voltage level of the pulse corresponded to 1.2 times the minimum boiling point at which bubbles began to form in the recording liquid. Accordingly, the tension became of the pulse selected to 24 V if the minimum boiling temperature corresponded to 20 V. The composition of the recording liquid was as follows.

Water 68 parts by weight

DÄG (diethylene glycol) 30 parts by weight black dye 2 parts by weight

The test operation of the recording system was carried out using the above-mentioned recording liquid and below the conditions set out above. The durability has been tested for various samples, and the results of the tests are given in Tables 3, 6, 9, 11, 13, 15, 17, 19, 21 and 23. The durability was assessed by counting the number of the electrical impulses that the recording head can withstand.

The characters "o" and "x" in these tables indicate that the

9
that the recording head can withstand 10 or more repeated pulse cycles or that the recording head can withstand only 10 cycles or less.

From these tables, it can be seen that the liquid jet recording head according to the present invention is excellent in durability and recording property over the comparative example shows. Although the result of the test carried out with the combination of type A and type 1-1 is special has been described, similarly excellent results of the liquid jet recording head of the invention were also obtained confirmed for other combinations of types.

Various examples of the liquid jet printing head of the present invention were prepared along with some comparative examples, and the deposition conditions for the formation of the heat-generating resistor film, the film thicknesses, the resistance values and the evaluation results are summarized in Tables 1-10. Examples P-I, P-2, P-3, P-4, S-I and S-2 in of Tables 1 to 3 are those having a resistive film having the composition of a-C: (X, H) type. The examples P-5, P-6, P-7, P-8, P-9, P-IO, P-II, P-12, S-3 and S-4 in Tables 4 through 6 are those using resistor films with the composition of the a-C: (X, H) -type with uneven distribution of atom X and / or atom H. Examples P-13, P-14, P-15, P-16, S-5 and S-6 in Tables 7 to 9 are those having resistance films of the composition of a-C: Si: (X, H) type. The examples P-17, P-18, P-19 and P-20 are those that are the resistance films of the construction of the a-C: Si: (X, H) type with uneven distribution have at least one of the Si atoms, X atoms and Η atoms. The examples P-21, P-22, P-23 and P-24 in Tables 12 and 13 are those having resistance films of a-C: Ge: (X, H) type construction. The examples P-25, P-26, P-27, P-28, P-29, P-30, P-31, and P-32 are those having resistance films of aC: Ge: (X, H) type construction with uneven Distribution of at least one of the Ge atoms, X atoms and Η atoms. Examples P-33, P-34, P-35 and P-36 in the tables 16 and 17 are those having resistor films of a-C: Si: Ge: (X, H) type composition. The examples P-37, P-38, P-39, P-40, P-41, P-42, P-43 and P-44 in Tables 18 and 19 are those showing resistance films of a composition of the a-C: Si: Ge: (X, H) -type with uneven distribution have at least one of Si atoms, Ge atoms, X atoms and Η atoms. the Examples P-45, P-46, P-47 and P-48 in Tables 20 and 21 are those using resistor films of a composition of the a-C: have (X, H) (p, n) -type. Finally, Examples P-49, P-50, P-51, P-52, P-53, P-54, P-55 and P-56 are those with resistive films having a composition of aC: (X, H) (p , n) types where

at least one component among the X atoms, Η atoms and the the electrical conductivity-controlling substance is unevenly distributed.

As indicated above, the same comparative example is given in all tables.

3518596

Table 1

example
No. Reaction gas Type A / B Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material PI CF./Ar
⁴ H ₂ 0.5
1 50
1 0.8 350 Glass P-2 CF./Ar
⁴ H ₂ 0.5
1 50
1 1.5 350 Glass P-3 CF./Ar
⁴ H ₂ 0.5
1 50
1 0.8 350 Si P-4 ^C 2 ^F 6 / ^Ar
H ₂ 0.5
1 50
1 1.5 350 Si

Table 2

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material S-I Type A / B 0.1 20th 5 350 Glass S-2 CHF ₃ / ar 0.1 20th 5 350 Si Reference
example CHF ₃ / ar 1 20th 1.6 200 Si Ar

Table 3

Example no. thickness
O
(A) resistance
(£) -. durability PI 1000 205 O P-2 1000 205 O P-3 1000 205 O P-4 1000 205 O S-I 1000 205 O S-2 1000 205 O Reference example 1500 120 X

Table 4

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material P-5 Type A / B 0.5
1 50
2 - 1 0.8 350 Glass P-6 CF./Ar
H ₂ 0.5
1 50
2 -> 1 1.5 350 Glass P-7 C ₉ F _fi / Ar
²⁶ H ₂ 0.5
1 50
1-2 0.8 350 Glass P-8 CF./Ar
⁴ H ₂ 0.5
1 50
1 * 2 1.5 350 Glass P-9 C _o F _fi / Ar
^{2 6} H ₂ 0.5
1 50
1 - 2 0.8 350 Si P-IO CF./Ar
⁴ H ₂ 0.5
1 50
1 - * 2 1.5 350 Si P-Il C ₂ F ₆ ZAr
H ₂ 0.5
1 ~ 50
2 -1 0.8 350 Si P-12 CF, / Ar
⁴ H ₂ 0.5
1 50
2 * 1 1.5 350 Si C ₉ F, / Ar
H ₂

Table 5

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material S-3 Type A / B 0.1 20 -> 10 5 350 Glass S-4 CHF ₃ / ar 0.1 20 * 10 5 350 Si Reference
example CHF ₃ / ar 1 20th 1.5 200 Si Ar

Table 6

Example no. thickness
O
(A) resistance
U) durability P-5 1000 230 O P-6 1000 230 O P-7 1000 230 O P-8 1000 230 O P-9 1000 230 O P-IO 1000 230 O P-Il 1000 230 O P-12 1000 230 O S-3 1000 230 O S-4 1000 230 O Reference example 1500 120 X

Table 7

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(WZcm ² ) Substrate
temperature
( ⁰ C) Substrate
material P-13 Type A / B 0.5
0.1 50
5 0.8 350 Glass P-14 CF./Ar
SiH ₄ ZAr 0.5
0.1 50
2 0.8 350 Glass P-15 C ₂ F ₆ ZAr
Si ₀ H _c / Ar
C D 0.5
O ₅ I. 50
5 0.8 350 Si P-16 CF / Ar
SiJ / Ar 0.5
0.1 50
2 0.8 350 Si C ₂ F ₆ ZAr
Si ₂ H ₆ / Ar

Table 8

example
No. Reaction gas Ratio AZB Throughput
lot
(SCCM) Electr.
power
(WZcm ² ) Substrate
temperature
(° C) Substrate
material S-5 Type A / B 0.5
0.1 15th
2 5 350 Glass S-6 CF ₄ ZAr
SiH ₄ ZAr 0.5
0.1 15th
2 5 350 Si Reference
example CF ₄ ZAr
SiH ₄ ZAr 1 20th 1.5 200 Si Ar

Table Ie 9 durability Example no. thickness
O
(A) resistance
(Λ) O P-13 1000 205 O P-14 1000 205 O P-15 1000 205 O P-16 1000 205 O S-5 1000 205 O S-6 1000 205 X Reference example 1500 120

Table 10

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
(° C) Substrate
material P-17 Type A / B 0.5
0.8 50
5 -> 2 0.8 350 Glass P-18 CF, / Ar
SiH ^ / Ar 0.5
0.8 50
5 0.8-0.9 350 Glass P-19 CF./Ar
SiHJ / Ar 0.5
0.8 50
5 + 2 0.8 350 Si P-20 CF-Mr
SiHj / Ar 0.5
0.8 50
5 0.8-0.9 350 Si CF./Ar
SiHJ / Ar

36Ί8596

Table 11

Example no. thickness resistance durability (A) (Ä) P-17 1000 230 O P-18 1000 230 O P-19 1000 230 O P-20 1000 230 O Reference example 1500 120 X

Table 12

example Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material P-21 Type A / B 0.5
0.1 50
5 0.8 350 Glass P-22 CF _d / Ar
GeH ^ / Ar 0.5
0.1 50
5 0.8 350 Glass P-23 C ₂ F ₆ ZAr
GeH ₄ / Ar 0.5
0.1 50
5 0.8 350 Si P-24 CF./Ar
GeHJ / Ar 0.5
0.1 50
5 0.8 350 Si C ₇ F _fi / Ar
GfeHj / Ar

Table 13

Example no. thickness
(A) resistance
{Si) durability P-21 1000 205 0 P-22 1000 205 0 P-23 1000 205 O P-24 1000 205 O Reference example 1500 120 X

Table 14

example
No. Reaction gas Ratio AZB Throughput
lot
(SCCM) Electr.
power
(WZcra ² ) Substrate
temperature
( ⁰ C) Substrate
materi al P-25 Type A / B 0.5
0.1 50
5 - »2 0.8 350 Glass P-26 CFJAr
GeH ₄ ZAr 0.5
0.1 50
5 * 2 0.8 350 Glass P-27 C ₂ F ₆ ZAr
GeH ₄ / Ar 0.5
0.1 50
5 0.8 ^ 0.9 350 Glass P-28 CF-ZAr
GeH ₄ ZAr 0.5
0.1 50
5 0.8 * 0.9 350 Glass P-29 C ₂ F ₆ ZAr
GeH ₄ ZAr 0.5
0.1 50
5 - »2 0.8 350 Si P-30 CF ₄ ZAr
GeH ₄ ZAr 0.5
0.1 50
5 * 2 0.8 350 Si P-31 C ₂ F ₆ ZAr
GeH ₄ ZAr 0.5
0.1 50
5 0.8-0.9 350 Si P-32 CF.ZAr
GeHJZAr 0.5
0.1 50
5 0.8-0.9 350 Si C ₂ F ₆ ZAr
GeH ₄ ZAr

IHSPECiED

Table 15

Example no. thickness
O
(A) resistance
(Sl) durability P-25 1000 230 O P-26 1000 230 O P-27 1000 230 O P-28 1000 230 O P-29 1000 230 O P-30 1000 230 O P-31 1000 230 O P-32 1000 230 O Reference example 1500 120 X

Table 16 Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr. Substrate Substrate example
No. Type A / B 0.5
0.1
0.05 50
5
5 power
(W / cm ² ) temperature
( ⁰ C) material P-33 CH./Ar
SiHVAr
GeHj / Ar 0.5
0.1
0.05 50
5
5 0.8 350 Glass P-34 CH./Ar
SiFT / Ar
GeFj / Ar 0.5
0.1
0.05 50
5
5 0.8 350 Glass P-35 CH./Ar
Si H./Ar
GeFj / Ar 0.5
0.1
0.05 50
5
5 0.8 350 Si P-36 CH./Ar
SiFT / Ar
GeFj / Ar 0.8 350 Si

Table 17

Example no. thickness
O
(A) resistance
(Ä) durability P-33 1000 205 O P-34 1000 205 O P-35 1000 205 O P-36 1000 205 O Reference example 1500 120 X

Table 18

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
materi al P-37 Type A / B 0.5
0.1
0.05 50
5 * 2
5 * 2 0.8 350 Glass P-38 CH./Ar
SiOAr
GeFj / Ar 0.5
0.1
0.05 50
5 - * 2
5 ^ 2 0.8 350 Glass P-39 CH./Ar
SiFT / Ar
GeH ^ / Ar 0.5
0.1
0.05 50
5
5 0.8 * 0.9 350 Glass P-40 CH./Ar
SiHT / Ar
GeFj / Ar 0.5
0.1
0.05 50
5
5 0.8 * 0.9 350 Glass P-41 CH./Ar
SiFT / Ar
GeH ^ / Ar 0.5
0.1
0.05 50
5 ^ 2
5 * 2 0.8 350 Si P-42 CH./Ar
SiHT / Ar
GeFj / Ar 0.5
0.1
0.05 50
5 * 2
5 * 2 0.8 350 Si P-43 CH./Ar
SiFj / Ar
GeHJ / Ar 0.5
0.1
0.05 50
5
5 0.8 * 0.9 350 Si P-44 CH./Ar
SiHT / Ar
GeFJ / Ar 0.5
0.1
0.05 50
5
5 0.8 * 0.9 350 Si CH./Ar
SiF ^ / Ar
GeHj / Ar

Table 19

Example no. thickness
(A) resistance
(£) durability P-37 1000 230 0 P-38 1000 230 0 P-39 1000 230 0 P-40 1000 230 0 P-41 1000 230 0 P-4E 1000 230 0 P-43 1000 230 0 P-44 1000 230 0 Reference example 1500 120 X

36Ί8596

Table 20

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material P-45 Type A / B 0.5 ₅
l-10 " ^b 50
125 1.5 350 Glass P-46 CF./Ar
PH ^ / Ar 0.5 ₅
1-10 50
125 1.5 350 Glass P-47 CF./Ar
B ₂ Hj / Ar 0.5 ₅
1-10 ° 50
125 1.5 350 Si P-48 CF _d / Ar
PH ^ / Ar 0.5 ₅
1.10 "° 50
125 1.5 350 Si CF./Ar
B ₂ Hg / Ar

Table 21

Example no. thickness
O
(A) resistance
(Ä) durability P-45 1000 180 O P-46 1000 180 O P-47 1000 180 O P-48 1000 180 O Reference example 1500 120 X

Table 22

example
No. Reaction gas Ratio A / B Throughput
lot
(SCCM) Electr.
power
(W / cm ² ) Substrate
temperature
( ⁰ C) Substrate
material P-49 Type A / B 0.5 _ ₅
1-10 ^D 50 ^ 30
125 1.5 350 Glass P-50 CF./Ar
PHyAr 0.5
1-10 ^b 50 -> 30
125 1.5 350 Glass P-51 CF./Ar
B ₂ H ^ / Ar 0.5 _ ₅
1-10 ^D 50
125 1.5-1.6 350 Glass P-52 CF, / Ar
PHpAr 0.5 ₅
1-10 ^b 50
125 1.5-1.6 350 Glass P-53 CF./Ar
B ₂ Hg / Ar 0.5 _ ₅
1-10 ^D 50 + 30
125 1.5 350 Si P-54 CF _d / Ar
PHg / Ar 0.5 _ ₅
1 * 10 ^D 50 - »30
125 1.5 350 Si P-55 CF _d / Ar
B ₂ H ^ / Ar 0.5 _ ₅
1-10 ^D 50
125 1.5-1.6 350 Si P-56 CF./Ar
PHg / Ar 0.5 ₅
1-10 ^D 50
125 1.5-1.6 350 Si CF./Ar
B ₀ HZ / Ar
C D

Table 23

Example no. thickness
O
(A) resistance
(ft) durability P-49 1000 205 O P-50 1000 205 O P-51 1000 205 O P-52 1000 205 O P-53 1000 205 O P-54 1000 205 O P-55 1000 205 O P-56 1000 205 O · Reference example 1500 120 X

· - - ^: ■ - ■ '■ ■ · ■ "- ■ 36Ί8596

A practical embodiment of a liquid jet recording system the invention incorporating the described liquid jet recording head will be described below. Figure 30 is a perspective view of a liquid jet recording system of the present invention with the wall partially cut away.

This recording system has two recording head units 70 which are mounted side by side on a carriage 72 and by Holder 71 are attached. Each recording head unit 70 is detachable and freely available so that it can be discarded when the recording liquid therein is used up.

A wire 82 running around the disks 80 and 81 is connected at both ends to the associated side surfaces of the carriage 72. The disk 81 is driven by a motor 84. The arrangement is such that the carriage 72 during operation of the engine 84 over the wire 82 is pulled so that it can move in Figure 30 along the guide body 74 to the left and right.

The roller 76 is carried by a rotating shaft 77, which in turn is driven by another motor through a gear mechanism 88 to feed the recording medium 78.

In operation, electrical signals corresponding to the information to be recorded are passed through a flexible conductor track 90 fed to the recording head units 70 so that the recording head units 70 radiate the droplets of the recording liquid towards the recording medium as indicated by the arrows Z, whereby the information is recorded on the recording medium.

It goes without saying that the recording head may be a full-line head be that extends over the entire length of the recording or

Print line extends. In such a case, unlike in the embodiment shown in FIG. 30, it is not necessary to to use a mechanism for driving the recording head.

Claims (43)

Claims 1. A liquid jet recording head having at least one liquid outlet for discharging a recording liquid for the formation of a jet of droplets of this liquid, characterized in that, that for the formation of the recording liquid droplets at least one electricity / heat conversion element with serves as a heat generating resistor film composed of a halogen atom and hydrogen atoms in a matrix of carbon atoms containing amorphous material. 2. A liquid jet recording head according to claim 1, characterized in that the amorphous material of the heat generating Resistance film next to the halogen atoms and hydrogen atoms also contains silicon atoms and / or germanium atoms and / or a substance that controls electrical conductivity. Dresdner Bank (Munich) Account 3939 844 Deutsche Bank (MQnchen) Account 2861060 Post office (Manchen) account 670-43-804 3. Liquid jet recording head according to claim 1 or 2, characterized in that the halogen atoms and / or the hydrogen atoms are unevenly distributed in the direction of the thickness of the heat generating resistor film. 4. Liquid jet recording head according to claim 2, characterized in that the halogen atoms and / or the hydrogen atoms and / or the silicon atoms and / or the germanium atoms and / or the ones controlling the electrical conductivity Substance have an uneven distribution in the direction of the thickness of the heat generating resistor film. 5. Liquid jet recording head according to one of claims 1 to 4, characterized in that the halogen atoms are the atoms of an element selected from the group consisting of F (fluorine), Cl (chlorine), Br (bromine), and I (iodine). 6. Liquid jet recording head according to one of the Claims 2 to 5, characterized in that the substance controlling the electrical conductivity is an element from the group III or Group V of the Periodic Table. 7. liquid jet recording head according to any one of claims 1 to 6, characterized in that the content of Halogen atoms is in the range of 0.0001 to 30 atomic percent. 8. A liquid jet recording head according to any one of Claims 1 to 6, characterized in that the content of hydrogen atoms in the range between 0.0001 and 30 atom% lies. 9. Liquid jet recording head according to claim or 2, characterized in that the sum of the contents of the halogen atoms and the hydrogen atom is in the range between 0.0001 and 40 atomic percent. 10. A liquid jet recording head according to claim 2, characterized in that the content of silicon atoms in the Range between 0.0001 and 40 atomic percent. 11. A liquid jet recording head according to claim 2, characterized in that the content of germanium atoms in the Range between 0.0001 and 40 atomic percent. 12. Liquid jet recording head according to claim 2, characterized in that the sum of the contents of the silicon atoms, Halogen atoms and hydrogen atoms in the range between 0.0001 and 40 atom%. 13. Liquid jet recording head according to claim 2, characterized in that the sum of the contents of the germanium atoms, Halogen atoms and hydrogen atoms in the range between 0.0001 and 40 atom%. 14. A liquid jet recording head according to claim 2, characterized in that the sum of the contents of silicon atoms, germanium atoms, halogen atoms and hydrogen atoms in the Range between 0.0001 and 40 atomic percent. 15. A liquid jet recording head according to claim 2, characterized in that the content of the electrical conductivity controlling substance in the range between 0.01 and 50,000 atomic ppm. 16. A liquid jet recording head according to any one of Claims 1 to 15, characterized in that the electricity / The heat converting element further has a protective layer. 17. A liquid jet recording head according to any one of Claims 1 to 16, characterized in that a plurality of recording liquid outlets are provided. 18. A liquid jet recording head according to any one of claims 1 to 16, characterized in that a plurality of electricity / heat conversion elements is provided. 19. Liquid jet recording system with the liquid jet recording head according to one of claims 1 to 18. 20. Liquid jet recording head with at least one liquid drop outlet for the delivery of a recording liquid to form a jet of this liquid, characterized in that with the liquid drop outlet at least one liquid channel is connected to a heating section and at least one electricity-to-heat converting element in the heating section is equivalent to, that is, a heat generating resistor film composed of a halogen atom and hydrogen atoms formed on a substrate an amorphous material containing carbon atoms and a pair of electrodes electrically connected to the resistive film includes. 21. A liquid jet recording head according to claim 20, characterized in that the amorphous material of the heat generating Resistance film in addition to the halogen atoms and hydrogen atoms also silicon atoms and / or germanium atoms and / or a contains the electrical conductivity controlling substance. 22. Liquid jet recording head according to claim 20 or 21, characterized in that the halogen atoms and / or the hydrogen atoms have an uneven distribution in the direction of the thickness of the heat generating resistor film. 23 liquid jet recording head according to claim 21 or 22, characterized in that the halogen atoms and / or the Hydrogen atoms and / or the silicon atoms and / or the germanium atoms and / or the one that controls electrical conductivity Substance have an uneven distribution in the direction of the thickness of the heat generating resistor film. 24. A liquid jet recording head according to any one of claims 20 to 23, characterized in that the halogen atoms are the atoms of an element selected from the group consisting of F (fluorine), Cl (chlorine), Br (bromine), and I (iodine). 25. Liquid jet recording head according to one of claims 21 to 24, characterized in that the electrical Conductivity-controlling substance an element from the Group III or Group V of the Periodic Table. 26. Liquid jet recording head according to one of claims 20 to 25, characterized in that the content of the Halogen atoms is in the range of 0.0001 to 30 atomic percent. 27. A liquid jet recording head according to any one of Claims 20 to 26, characterized in that the content of hydrogen atoms in the range between 0.0001 and 30 atom% lies. 28. A liquid jet recording head according to any one of Claims 20 to 27, characterized in that the sum of the contents of halogen atoms and hydrogen atoms in the range is between 0.0001 and 40 atomic percent. 29. A liquid jet recording head according to claim 21, characterized in that the content of silicon atoms in the Range between 0.0001 and 40 atomic percent. 30. A liquid jet recording head according to claim 21, characterized in that the content of germanium atoms in the Range between 0.0001 and 40 atomic percent. 31. A liquid jet recording head according to claim 21, characterized in that the sum of the contents of silicon atoms, halogen atoms and hydrogen atoms in the range between 0.0001 and 40 atom-Z lies. 32. Liquid jet recording head according to claim 21, characterized in that the sum of the contents of the germanium atoms, Halogen atoms and hydrogen atoms in the range between 0.0001 and 40 atom%. 33. A liquid jet recording head according to claim 21, characterized in that the sum of the contents of the silicon atoms, Germanium atoms, halogen atoms and hydrogen atoms in the range between 0.0001 and 40 atom%. 34. A liquid jet recording head according to claim 21, characterized in that the content of the electrical conductivity controlling substance is in the range between 0.01 and 50,000 atomic ppm. 35. A liquid jet recording head according to any one of Claims 20 to 34, characterized in that the electrothermal conversion element further has a protective layer. 36. Liquid jet recording head according to one of claims 20 to 35, characterized in that a plurality of liquid channels and a plurality of liquid outlets corresponding to the liquid channels is provided. 37. A liquid jet recording head according to any one of claims 20 to 36, characterized in that a plurality of liquid outlets and a single liquid channel common to the liquid outlets is provided. 38. A liquid jet recording head according to claim 36, characterized in that it has a common ink chamber, with which the fluid channels are in communication. 39. A liquid jet recording head according to claim 36, characterized in that the heating sections of the liquid passages are connected to each other. 40. A liquid jet recording head according to any one of
Claims 20 to 39, characterized in that the heat generating resistive film on the substrate and the pair of electrodes
is formed resting on the substrate. 41. A liquid jet recording head according to any one of
Claims 20 to 39, characterized in that the pair of electrodes on the substrate and the heat-generating resistive film
is formed resting on the substrate. 42. A liquid jet recording head according to claim 40, characterized in that the pair of electrodes is covered by a protective layer. 43. Liquid jet recording system having a
A liquid jet recording head according to any one of claims 20 to 42.