CN1201933C - Heating resistor and manufacturing method thereof - Google Patents
Heating resistor and manufacturing method thereof Download PDFInfo
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- CN1201933C CN1201933C CN 00800849 CN00800849A CN1201933C CN 1201933 C CN1201933 C CN 1201933C CN 00800849 CN00800849 CN 00800849 CN 00800849 A CN00800849 A CN 00800849A CN 1201933 C CN1201933 C CN 1201933C
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1623—Manufacturing processes bonding and adhesion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14016—Structure of bubble jet print heads
- B41J2/14088—Structure of heating means
- B41J2/14112—Resistive element
- B41J2/14129—Layer structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1601—Production of bubble jet print heads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1626—Manufacturing processes etching
- B41J2/1628—Manufacturing processes etching dry etching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1631—Manufacturing processes photolithography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/164—Manufacturing processes thin film formation
- B41J2/1646—Manufacturing processes thin film formation thin film formation by sputtering
Abstract
The invention relates to a heating resistor with a non-metallic materials, which emits heat by electric current applied thereto, comprising at least tantalum (Ta), silicon (Si), oxygen (O), and nitrogen (N). In a case where such heating resistor has mole ratio Si/Ta of 0.35<Si/Ta<0.80, oxygen mol% of 25 mol% to 45 mol%, and nitrogen mol% of 5 mol% to 25 mol%, the heating resistor shows resistivity equal to or greater than 4 m OMEGA cm, peak angle of X-ray diffraction strength is equal to or smaller than 37.5 degrees, and has resistance over 100,000,000 pulses. The heating resistor having the above characteristics is suitable for a print head of a thermal ink-jet printer. Further, the heating resistor shows stable but high resistivity, after the heating resistor is annealed.
Description
Technical field
The method that the present invention relates to heating resistor and make this heating resistor.More specifically, the present invention relates to the method that has the heating resistor of stable high resistivity and make this heating resistor, the resistivity of described heating resistor moves with heat hardly, also has excellent cavitation resistance simultaneously, therefore is suitable in the temperature-sensitive ink-jet printer.
Background technology
The influence that conventional heating resistor can be heated shows unsettled resistivity.More precisely, having more, the resistance of high resistivity just is easier to show unsettled resistivity.The feasible control resistor that is difficult to of these unsettled resistivity, and particularly like this when using the heat energy of resistor.
Conventional heating resistor uses following element to form usually: oxide; Nitride; Oxide/nitride; Oxide/nitride/metal; Oxide/nitride/metal/other materials, or the like.According to these compositions, many materials have been proposed.For example, Si-N-Ir-(Ru), Si-N-Ir-(Pt), Si-N-Ir-Ru-Pt, Si-O-Ir-(Ru), Si-O-Ir-(Pt), Si-O-Ir-Ru-Pt, Si-C-Ir-(Ru), Si-C-Ir-(Pt), Si-C-Ir-Ru-Pt, or the like.
Material with above-mentioned composition does not have help for reducing the change in resistance that is caused by thermal conductance.In other words, many situations that need the heat energy of heating resistor can not tolerate the change in resistance of conventional heating resistor.
On the contrary, be extensive use of the temperature-sensitive ink-jet printer, and wherein manyly all in its printhead, used heating resistor.Using in the temperature-sensitive ink-jet printer has the side to spray (side shooter) type printhead and top jet (roof shooter) type printhead.Side ejection-type printhead is at the direction parallel with the area of heating surface of heating resistor ejection ink, and top jet type printhead is at the direction ejection ink perpendicular to the area of heating surface of heating resistor.
Figure 1A-1C is the sectional view that schematically shows side ejection-type printhead, and Fig. 1 D-1F is the sectional view that schematically shows top jet type printhead.Shown in Figure 1A or 1D, heating resistor is formed on the silicon base 1, and perforated panel 3 is towards silicon base 1.Label 4 expression nozzles.In the ejection-type printhead of side, shown in Figure 1A, the slit between silicon base 1 and the perforated panel 3 forms nozzle 4 at their side, and shown in Fig. 1 D, the nozzle 4 of top jet type printhead is formed on the heating resistor 2.In above-mentioned two kinds of structures, heating resistor 2 is connected with the electrode (not shown), and the slit between silicon base 1 and the perforated panel 3 forms the ink via 5 that ink is provided.
From printhead, spray ink droplet according to following steps (1)-(5).(1) when the electric current of representative graph image data flow through in by heating resistor 2, resistor 2 heated ink water layers made its boiling, therefore occur steam core (Figure 1B or 1E) on heating resistor 2.(2) the steam core flocks together, and forms steam bubble 6 thus.(3) along with the expansion of steam bubble 6, it by releasing in the nozzle 4, form ink droplet 5-2 in the tip of nozzle 4 thus, and the pressure of steam bubble forces ink droplet to drop in (Fig. 1 C or 1F) on the paper with ink 5-1.(4) steam bubble shrinks.(5) steam bubble 6 fragmentations, and the suction force that is produced is used for new ink extraction to heat next time.Above-mentioned steps (1)-(5) are to finish in the very short time.
The effect that is produced by above-mentioned steps (1)-(3) realizes by film boiling.The film boiling phenomenon normally takes place under following situation: highly the article of heating are immersed in (for example iron quenching) in the liquid, the surface of perhaps violent heating and the contacted article of liquid.A kind of origin cause of formation after the most ink-jet printer utilization.As the result of film boiling, behind bubble breaking, produce swabbing action.These swabbing actions are called cavitation erosion.
Fig. 2 A schematically shows steam bubble length by length by being formed into broken figure.In such cases, heating resistor 2 is placed in the opening pond that the degree of depth is 1mm.Produce fragmentation from steam bubble and need 6 microseconds.Fig. 2 A has shown the steam bubble when a microsecond, and Fig. 2 B has shown the time control that is applied to the electric current on the heating resistor 2.
Shown in Fig. 2 B, electric current flows through from heating resistor 2 needs 1 microsecond, and heating resistor 2 is thus at the phase I of 1 microsecond heating ink.In the next 1 microsecond stage, steam bubble appears, and it releases ink droplet, and shrinks immediately before the time that arrives 3 microseconds.In case steam bubble begins to shrink, the steam bubble pressure inside will descend fast, and broken fully when 6 microseconds.Negative pressure cavitation erosion shown in arrow a-1, a-2 and the a-3 among pressure decline generation Fig. 2 A.
Negative pressure cavitation shock heating resistor 2 is with its tractive that makes progress.If the degree of depth in above-mentioned opening pond is 1mm, upwards the power of tractive heating resistor 2 will reach 1000ton/cm
2In ink-jet printer, the heating resistor in the printhead is about 40 square microns, and impulsive force will be 16kg thus.
Heating resistor need have the resistivity enough bigger than predeterminated level.Predeterminated level need send the lowest resistivity of desirable heat energy when maximum current, and high maximum current can tolerate in the circuit that drives heating resistor.Drive circuit in the monolithic type printhead is arranged on the identical plate with heating resistor, and the transistorized maximum current of driver is about 100mA in the printhead of the type.In the case, needed resistivity is equal to, or greater than 4m Ω cm.Generally, so big resistivity is impossible for metal resistor.
The needed heating resistor of temperature-sensitive ink-jet printer should meet the following conditions: (1) resistivity-and or not the typical resistivity that metal resistor has, that is to say the big resistivity that is equal to, or greater than 4m Ω cm, more preferably be equal to or greater than 5m Ω cm.(2) the change in resistance rate that heat resistanceheat resistant stability-Re causes is equal to or less than 0.05%/℃, more preferably approach 0%/℃.(3) cavitation resistance-in opening pond experiment, tolerate 100,000,000 subpulse.
For resistivity, if the maximum current of driver transistor is about 100mA, the electric work of each pulse is 1W, and needed resistance value is 100 Ω.Most heating resistor is a metal resistor, and therefore conventional resistivity is equal to or less than 1m Ω cm.
The temperature-sensitive ink-jet printer uses square heating resistor usually.If the resistivity of resistor is equal to or less than 1m Ω cm, need the thickness of square heating resistor to be about 100nm, to send desirable heat energy.100nm is thick too thin for resistor was had for the long life-span.
The material that known group becomes Ta-Si-O or similar composition is the suitable material of heating resistor, and this is because they have more excellent relatively characteristic.But, wait the life-span of the heating resistor that material makes when 4m Ω cm resistivity, can not reach desired horizontal thus.More precisely, heating resistor can not tolerate 100,000,000 subpulse in the experiment of the opening pond of water.Worse, the change in resistance rate that heat causes is 0.05%/℃, still big than permissible level.
Under these conditions, the heating resistor of being made by the Ta-Si-O material is when being used for ink-jet printer, and film needs protection.Diaphragm makes heating resistor avoid the corrosion of ink and the damage of cavitation erosion.Diaphragm covering heating resistor with about 1 micron thickness has hindered the heat energy that resistance sent.Because these output losses need more energy, so conventional Ta-Si-O heating resistor almost can not satisfy the requirement of energy savings.
Disclosure of the Invention
The purpose of this invention is to provide a kind of heating resistor, it has high resistivity, low rate of change and the excellent cavitation resistance of being heated, and is suitable for thus in the temperature-sensitive ink-jet printer.
Above-mentioned purpose realizes that by a kind of heating resistor this resistance sends heat energy when applying electric current.
Described heating resistor (12) comprises that tantalum (Ta), silicon (Si), oxygen (O) and nitrogen (N) are as component at least.
So the heating resistor that constitutes is suitable in the temperature-sensitive ink-jet printer, and this is because it shows stable high resistivity as nonmetallic materials, but the change in resistance that causes of being heated is little, and equally with metal material has an excellent cavitation resistance.
In this heating resistor, the mol% of nitrogen (M2) is 5mol%≤M2≤25mol%.In the case, the mol of Si/Ta ratio is 0.35＜Si/Ta＜0.80, and the mol% of oxygen (M1) is 25mol%≤M1≤45mol% in addition.
In above-mentioned the setting, only can select the Si/Ta mol ratio of 0.35＜Si/Ta＜0.80, only can select the oxygen mol% (M1) of 25mol%≤M1≤45mol% in addition.
Heating resistor can comprise impalpable structure, and the broad peak value angle of the X ray intensity that wherein occurs in the X-ray diffraction is 37.5 degree, and resistivity is equal to, or greater than 4m Ω cm.
In addition, heating resistor can comprise impalpable structure, and the absorption coefficient of light when wherein light energy is 0.5-1eV is 70000/cm or lower, and resistivity is equal to, or greater than 4m Ω cm.
Heating resistor (12) can be used in the printhead of ink-jet printer.In the case, heating resistor (12) can directly contact ink, and produces bubble in ink.Therefore, the printhead of temperature-sensitive ink-jet printer has higher energy efficiency and excellent cavitation resistance for better drop output.
Another object of the present invention provides the method for making heating resistor, and this resistance has high resistivity, low be heated rate of change and excellent cavitation resistance, and is suitable for thus in the temperature-sensitive ink-jet printer.
Said method is to realize by the method for making heating resistor (12), and is heatable when this heating resistor applies electric current thereon, said method comprising the steps of:
Go up the film (12) that formation is made by Ta-Si-O-N in substrate (11); And
Described Ta-Si-O-N film forms heating resistor (12) by annealing.
In said method, annealing can be carried out in air.In the case, annealing steps can be finished easily.
In said method, annealing can be carried out in inert gas.In the case, just can prevent that electrode film is oxidized during annealing, so the problem that oxidation produced can not take place.
If heating resistor is the printhead that is used for the temperature-sensitive ink-jet printer, the temperature during the annealing can be 350-600 ℃.
If the printhead of temperature-sensitive ink-jet printer is the printhead of monolithic type, wherein printhead is installed on the identical silicon base with drive circuit, and then the temperature during the annealing can be 350-450 ℃.
In said method, annealing can be carried out 10-30 minute.
The Ta-Si-O-N film can have diaphragm (21) thereon.In the case, anneal when the Ta-Si-O-N film can have diaphragm thereon, and annealing can be carried out in air.Therefore can prevent that electrode film etc. is oxidized.
The accompanying drawing summary
After reading following the detailed description and the accompanying drawings, above-mentioned purpose of the present invention with and other objects and advantages will become more obvious, in the accompanying drawings:
Figure 1A, 1B and 1C schematically show the figure that one step of ink connects step ground injection, and it is used for the operating principle of interpretation routine side ejection-type printhead;
Fig. 1 D, 1E and 1F schematically show the figure that one step of ink connects step ground injection, and it is used for the operating principle of interpretation routine top jet type printhead;
Fig. 2 A is the figure that is schematically illustrated in the opening pond experiment every the observed Bubble Formation Process of 1 microsecond, and Fig. 2 B is presented in the experiment of opening pond electric current by the figure of the time control of passing through in the heating resistor:
Fig. 3 is schematically illustrated in according to the thermal treatment zone in the printhead of the temperature-sensitive ink-jet printer of one embodiment of the invention and the sectional view of peripheral structure;
Fig. 4 is the composition of three kinds of typical heating resistor samples and the table of resistivity;
Fig. 5 is the figure that is used to explain basis of the present invention, has shown the Ta-Si-O film with different ratio of components and the resistivity and the relation between the peak value angle that occurs behind the X-ray diffraction of Ta-Si-Al-O film;
Fig. 6 is the figure that shows wherein a kind of X-ray diffraction result of Ta-Si-O-N material;
Fig. 7 shows the Ta-Si-O shown in Ta-Si-O-N material and Fig. 5 and the Ta-Si-Al-O material figure in peak value angle behind the X-ray diffraction and the relation between the resistivity;
Fig. 8 shows the resistivity of Ta-Si-O-N film and the figure of the relation between the temperature, is used for comparing with routine techniques;
Fig. 9 is the figure that shows the light absorption characteristics that is formed on the Ta-Si-O-N film on the silicon base;
Figure 10 is the figure that shows the result of a plurality of heating resistors in the experiment of opening pond who is made by sample shown in Figure 41;
Figure 11 is the figure that shows the result of a plurality of heating resistors in the experiment of opening pond who is made by sample shown in Figure 42;
Figure 12 lists the closed cell result of experiment of use sample 2 and the table of opening pond result of experiment;
Figure 13 lists 11 kinds of tables with Ta-Si-O-N film sample of different ratio of components, comprising sample 1-3 shown in Figure 4 and other sample 4-11;
Figure 14 shows that the result with sample 4-11 adds the peak value angle of the sample 1-11 that obtains behind the figure shown in Figure 7 and the figure of the relation between the resistivity;
Figure 15 shows through the Ta-Si-O-N film of annealing and figure without the change in resistance of the film of annealing;
Figure 16 shows through the heating resistor of annealing with without SST (stress increases experiment, the Step-up Stress Test) result's of the heating resistor of annealing figure;
Figure 17 is the sectional view that schematically shows according near the structure the thermal treatment zone in the printhead of the temperature-sensitive ink-jet printer of one embodiment of the invention;
Figure 18 A, 18B and 18C connect the sectional view of manufacture method that the printhead of temperature-sensitive ink-jet printer is as shown in figure 17 explained on a step ground one step;
Figure 19 is the figure that is presented at the relation between the increment rate of annealing temperature under 4 kinds of different conditions and annealing rear surface resistivity; And
Figure 20 is presented at the annealing in process time and the figure of the relation between the relative resistance rate afterwards that anneals under 4 kinds of different conditions.
Implement best mode of the present invention
Description explanation the preferred embodiments of the invention.
Fig. 3 is the sectional view that schematically shows printhead, the particularly thermal treatment zone and peripheral structure thereof.Printhead 10 shown in Fig. 3 is so-called top jet type printheads.Unshowned part is that thickness is the oxide skin(coating) (SiO of 1-2 micron in the printhead 10
2), it is formed on the surface of substrate 11.
What label 12 was represented is the heater resistor films of being made by at least 4 component Ta (tantalum), Si (silicon), O (oxygen) and N (nitrogen), and it is formed on the oxide skin(coating) by film formation technology.Heater resistor films 12 is to form pattern with photoetching technique, to have shape of stripes.The finished electrode film of being made by gold etc. also has the striped sheet.The sheet of strip electrode film is deposited on the heater resistor films 12, so that the pair of electrodes sheet covers the two ends of a slice heating electrode film 12, exposes the core of every heating electrode film 12 thus.When forming electrode film, form the screen layer of making by Ti-W, make this screen layer between electrode film and heater resistor films 12.The exposed region of heater resistor films 12, promptly, the zone that do not covered by electrode film, as the thermal treatment zone 13.Each to electrode slice in, electrode slice will be as single electrode 14, and another will be as ordinary electrode 15.
After forming the thermal treatment zone 13, coating organic material such as polyimides are as pre-wall (to-be-wall) layer on substrate 11, and its thickness is about 20 microns.The pattern of pre-parietal layer forms by photoetching technique, and this layer is retained on the single electrode 14, and substrate 11 is cured, and wherein to be exposed to temperature be under 300-400 ℃ the heat 30-60 minute to substrate 11.Form the wall of being made by light-sensitive polyimide 16 thus on single electrode 14, it highly is about 10 microns.
After forming the thermal treatment zone 13 and wall 16, deposition perforated panel 17 is as top layer on substrate 11.Use metal mask (not shown) etching (dry ecthing) perforated panel 17 then, to form nozzle 18 in the perforated panel on the thermal treatment zone 13 17.The interval of nozzle 18 is less, for example is about 40 microns.Because perforated panel 17 is formed on the wall 16, so perforated panel 17 is separated with ordinary electrode 15.The distance (its height with wall 16 is identical) that highly is 10 microns is as ink via 19.Ink provides in the space to the thermal treatment zone 13 via ink via 19.
As shown in Figure 3, the thermal treatment zone 13 exposes, and in other words, does not have protective layer etc. thereon.In the printhead of the type, use protective layer usually, and thickness is not less than 1 micron.There is not the structure of protective layer to improve the energy efficiency that is used for the ink ejection greatly.
As mentioned above, the component of heater resistor films 12 is at least Ta, Si, O and N.The preferable range that element is formed is as follows.The mol ratio of Si/Ta is 0.35＜Si/Ta＜0.80, more preferably 0.35＜Si/Ta＜0.45.M1 (mol% of oxygen) is 25mol%≤M1≤45mol%.M2 (mol% of nitrogen) is 5mol%≤M2≤25mol%.
Heating resistor according to the present invention is characterised in that having 4 elements that comprise Ta, Si, O and N forms.This structure is based on the advanced configuration of the conventional Ta-Si-O of composition, and it demonstrates more excellent performance for heating resistor.It is the result that test has the sample of various Ta-Si-O and other elements composition in experiment that above-mentioned 4 elements are formed.
Fig. 4 has shown the table of the composition of typical 3 kinds of samples, and these samples have 4 elements to be formed, and is the experiment product that is used to test.As shown in Figure 4, the component of sample is Ta, Si, O and N.This table has shown the mol ratio of mol%, the Si/Ta of each element, mol% and the resistivity (m Ω cm) of O+N.
Because the result shown in this table has admissible error, so the summation of the mol% of 4 kinds of elements just is not 100%.That is to say that total mol% of sample is as follows.Sample 1:100.1%, sample 2:99.7%, and sample 3:100.6%.
Fig. 5 is the figure that explains the characteristic of 4 element heating resistors of the present invention.The figure illustrates characteristic curve, these lines have been represented the relation between peak value angle 2 θ and resistivity behind the X-ray diffraction of 8 samples respectively.Sample comprises material and 2 materials that Ta-Si-Al-O forms that 6 Ta-Si-O form, and they have different ratio of components respectively.θ represents the angle of reflection of Bragg reflection, and the angle of the broad peak of X-ray diffraction intensity is represented at the peak value angle.In the figure, transverse axis is represented peak value angle 2 θ (degree), and vertical pivot is represented the resistivity (m Ω cm) of logarithm level.
Line " a " is represented the feature of the sample of 6 Ta-Si-O compositions, and line " b " is represented the feature of the sample of 2 Ta-Si-Al-O compositions.Line " a " and line " b " all show between peak value angle 2 θ and the resistivity and have dependency relation.By these experiments, peak value angle 2 θ can and reduce along with the increase of oxygen amount.Following this phenomenon of having studied of inventor of the present invention.
Above-mentioned broad peak shows in the material with impalpable structure usually.The appearance of these broad peaks is the reflections in structure factor (reciprocity space), and this structure factor has been represented the order of nearest atom.For example, three elements (A, B and C) compound structure factor as a whole is A-A, A-B, B-B, A-C, B-C and the C-C summation of totally 6 structure factors.The Fourier of the structure factor of compound transforms the average atom order that produces wherein.
Therefore, the average atom order has been reflected at the peak value angle.That is to say that as shown in Figure 5, peak value angle 2 θ are relevant with resistivity.According to the relation between this fact and oxygen amount and peak value angle 2 θ, inventor of the present invention reasons out, and distance and configuration between the average atom of cation and anion (oxygen) (as Ta-O, Si-O and Al-O) might be reflected in the peak value angle.This inference points out further that distance also depends on oxygen density between the average atom of Ta-Ta and Ta-Si, so distance between the average atom of Ta-Ta and Ta-Si is also reflected at the peak value angle.
This inference is consistent with the result shown in Fig. 5.Among Fig. 5, the point of representing the Ta-Si-Al-O sample is along with resistivity descends and disperses (lower right among the figure) along characteristic curve " a ".This fact can prove by the following fact: resistivity is low more, and the influence that order produced between cation is just big more, and this is to reduce because the quantity of anion reduces with resistivity.
Therefore, the connection between the nearest atom has been reflected at the peak value angle that obtains in the X-ray diffraction.This fact prompting, the intensity and the cavitation resistance of heating resistor might be reflected in the peak value angle.In addition, resistivity might reflect the band structure of sample, just the connection between the atom.
The inventor is also noted that the following fact: characteristic curve " a " and " b " are not parallel to each other.More precisely, along with peak value angle 2 θ increase (near the right-hand member of figure), characteristic curve " b " (Ta-Si-Al-O) shows than (Ta-Si-O) bigger resistivity (in the upper end of figure) of characteristic curve " a ".
This fact might be since the valence link number of Al less than the valence link number of Si and Ta.In the case, Si is 4 valency atoms, and Ta is 5 valency atoms, and Al is 3 valency atoms.According to this inference, the inventor concentrates on the element that changes the valence link number.In fact, observed the increase along with Si in the Ta-Si-O material, resistivity also increases.This fact shows that the material that is rich in Si trends towards having bigger resistivity along with the increase at peak value angle.
The inventor will form the combination that Ta-Si-O and Ta-Si-Al-O are considered as cation and anion, promptly, (Ta-Si)-O and (Ta-Si-Al)-O, and draw following inference.
In addition, if the valence link number of atom is more little in the material, it demonstrates higher resistivity more.Moreover, because the electronics that is equal to or less than in the material that 37.5 degree have high resistivity when (atypical scope in the metal resistor) at the peak value angle is localization, may be strong so the chemistry in the material is connected with.This fact shows that material has higher cavitation resistance.
The rate of change that is heated (temperature coefficient) that the inventor also observes resistivity in the material with small leak angle is little.
According to the above-mentioned fact, the material with high resistivity and small leak angle is suitable for heating resistor of the present invention.Metal typical heating resistor has little resistivity thermal change rate, but will not have the high resistivity that is suitable for heating resistor.So the inventor draws following inference: nonmetallic materials might have littler peak value angle and the resistivity of Geng Gao.
In addition, preferable material should have other anion elements ((Ta-Si)-(O-β)), ((Ta-Si-Al)-O) for (Ta-Si-α)-O material, was difficult to resistivity is increased to 4m Ω cm when peak value angle 2 θ hours obviously as can be seen because from characteristic curve " b ".If the valence link number be negative 3 nitrogen as the anion element, then this material can show high resistivity, this is because the valence link number of oxygen is negative 2.When its prompting is equal to or less than 37.5 degree (atypical scope in the metal material) as peak value angle 2 θ, this material will have the resistivity that is equal to, or greater than 4m Ω cm.Based on above-mentioned inference, the inventor has prepared the film that the material be made up of Ta-Si-O-N is made, wherein the striped target of sputter Ta and Si by DC sputter under the mixed atmosphere of Ar, O and N.
Sputter is carried out under the following conditions.Final pressure: 0.5 * 1.33 * 10
-4Pa, sputtering power: 1kW, film formation rate: 2.4nm/min, wherein a Si substrate is used for analyzing in identical chamber, and another Si substrate is used for the experiment of pulse tolerance, in a back substrate 1 micron SiO is arranged
2Layer.
Behind the Ta-Si-O-N film that annealing so forms, character such as the rate of change that is heated through resistivity, the resistivity of stable heating resistor are stable, that is to say their not times to time change.
Fig. 6 is the figure that shows the X-ray diffraction analysis result of Ta-Si-O-N film (sample 3 among Fig. 4).The X-ray diffraction intensity figure that this figure shows has single broad peak, and on behalf of this film, it have impalpable structure.The unit of X-ray diffraction intensity is an arbitrary unit.
Fig. 7 shows that as shown in Figure 43 have the position, peak value angle of Ta-Si-O-N sample film of different ratio of components and the figure of the relation between the resistivity.This figure also illustrates characteristic curve " a " (Ta-Si-O) and characteristic curve " b " (Ta-Si-O-N) as a reference.Can obviously find out from this figure, the result of 3 related samples be equal to or less than at the peak value angle 37.5 the degree and resistivity is equal to, or greater than in the zone of 4m Ω cm.This result shows that these materials are suitable for use as the heating resistor in the temperature-sensitive ink-jet printer.
The ratio of components of 3 samples is as shown in Figure 4 analyzed the suprabasil heater resistor films of Si by RBS (Rutherford reflects spectroscopy) and is obtained.Because RBD can detect lighter nitrogen hardly, thus the nitrogen content in the relatively low sample 1 and 2 of nitrogen content with ESCA (chemical analysis electronic spectrum) detection, this ESCA is a kind of in the photoelectron spectroscopy.
Fig. 8 shows the resistivity of the heating resistor (Ta-Si-O-N) of sample 2 among Fig. 4 and the figure of the relation between the temperature.Also shown is the relation of two conventional materials (Ta-Si-O).In the figure, the relation of characteristic curve " d " representative sample 2, and the result of the conventional Ta-Si-O heating resistor of characteristic curve " e " representative, its resistivity at room temperature is 4m Ω cm, characteristic curve " f " is represented the result of another conventional Ta-Si-O heating resistor, and its resistivity at room temperature is 2m Ω cm.The transverse axis representation temperature of this figure (℃), and the ratio of the changes in resistance rate " R (T) " under resistivity under its vertical pivot stands for room temperature " R (room temperature) " and the temperature T.
These materials are formed on the silicon base in identical measurement chamber.The figure of this material is identical when testing with above-mentioned opening pond.Each Ta-Si-O-N heater resistor films is 40 square microns.
Resistivity is following obtaining: measure the voltage that is applied on the heating resistor, have electric current to pass through in this resistance.Use the DVM measuring voltage.Temperature changes with electric current.With infrared emission thermometer measure temperature, this thermometer can be measured the temperature on the zonule.As shown in Figure 8, the resistivity of the Ta-Si-O-N heating resistor rate of change that is heated, with characteristic curve " d " expression, be 10% under 400 ℃ (0.025%/℃), and resistivity is equal to, or greater than 5m Ω cm.Instead, the resistivity of the represented conventional material of characteristic curve " e " and " f " rate of change that is heated is bigger 2 times or more than characteristic curve " d ".
Fig. 9 is the figure that is presented at the light absorption characteristics of the Ta-Si-O-N heater resistor films that forms on the silicon base.Inventor of the present invention concentrates on light absorption characteristics, to observe the feature of Ta-Si-O-N heater resistor films from different angles.This figure demonstrates the absorption coefficient of light, obtains and the coefficient of gained is per sample light transmission, and the ratio of components of this sample is identical with the sample 2 shown in Fig. 4 and have thickness arbitrarily.
The transverse axis of figure shown in Fig. 9 is represented luminous energy (eV), and its vertical pivot is represented the absorption coefficient of light (cm
-1).According to this figure, the absorption coefficient that obtains when energy range is 0.5-1eV is little (being equal to or less than 70000/cm), and in 1eV or more high-octane high-energy zone, absorption coefficient increases gradually.Can find out obviously that from Fig. 9 the absorption coefficient of gained is kept off in 0, and not have tangible light slit.
Shown light absorption characteristics shows on the whole has band gap to exist.That is to say, similar by heating resistor and degeneracy semiconductor that sample among Fig. 42 makes, this be because optical signature and little temperature coefficient (resistivity be heated rate of change be equal to or less than 0.025%/℃).In other words, heating resistor is similar to the degeneracy semiconductor that the Energy distribution of carrier (free electron or hole) is degeneracy Fermi distribution.
Carry out the experiment of opening pond then with the assessment cavitation resistance.In this experiment, preparation is formed on the Ta-Si-O-N material on the silicon base of oxidation in identical chamber, wherein is formed with the sample 1 shown in Fig. 4, and W-Ti film that is formed for connecting up then on this material and Au film then form pattern.
The prepared heating resistor that is used for the experiment of opening pond is 25 square microns, and thickness is 480 microns.Applying frequency on heating resistor is 10kHz and the pulse with 1 microsecond pulse width.Frequency and pulse width are to determine according to the ink output performance of ink jet-print head, and this printhead uses the prototype heating resistor of making under the same conditions.
Figure 10 is result's the figure of the opening tank experiments of show sample, and this sample is to form in forming the identical chamber of sample shown in Figure 41.The umber of pulse that the transverse axis representative of figure shown in Figure 10 is applied, and its vertical pivot is represented resistance value (Ω).As shown in figure 10, neither one produces broken string after applying pulse 100,000,000 time in 9 heater elements (ch00-ch64), that is to say to obtain excellent result.In addition, tangible damage is not observed with electron microscope in the experiment back.
Figure 11 is result's the figure that shows the opening tank experiments of another sample, and this sample is to form in the chamber identical with forming sample shown in Figure 42.The umber of pulse the same with Figure 10, that the transverse axis representative of figure shown in Figure 11 is applied, and its vertical pivot is represented resistance value (Ω).Figure 11 has shown and is applying the situation of pulse when line disconnects on the sample.In 9 heater elements (ch00-ch64), as shown in figure 11, find that after applying pulse 200,000,000 time line disconnects for the first time.
As everyone knows, opening pond experiment is a kind of in the most harsh experiment, and it is a kind of test of almost destruction property.The ability of heating resistor tolerance 100,000,000 subpulse shows that this heating resistor has the needed lasting durability of ink-jet printer.
As shown in Figure 4, having the sample 1 of excellent cavitation resistance and 2 resistivity is 5m Ω cm or higher.This is far above the needed mean value of heating resistor in the ink jet-print head.
Inventor of the present invention has also made another prototype printhead with their inference of certain proof.This prototype is to be made by the material in the chamber identical with sample 2.The nozzle of prototype printhead is formed in the perforated panel, and this perforated panel is formed on the wall.Make printhead output water and ink, observe the damage of the heating resistor of making by sample 2 thus from the angle of anti-cavitation erosion.The opposite closed cell that is called with the opening pond of this experiment is tested.
Figure 12 is the table that shows the result of closed cell experiment and opening pond experiment (sample 2 makes water).No matter have or not the diaphragm structure, the heating resistor of being made by sample 2 can tolerate 200,000,000 subpulse in the experiment of opening pond, and can tolerate 1,000,000,000 subpulse in the closed cell experiment.These results have reached target (is 100,000,000 subpulse, is 1,000,000,000 subpulse) in the closed cell experiment in the experiment of opening pond.
If use ink (black ink), the pulse that is applied is limited in about 300,000,000 time, and this is because the damage of material rather than the damage of heating resistor.But, after experiment, observe heating resistor immediately, do not find to damage.
Therefore prove that the heater resistor films with Ta-Si-O-N composition demonstrates the excellent specific property of the printhead that is used for ink-jet printer.Inventor of the present invention has also prepared several Ta-Si-O-N resistor films, and their ratio of components is different mutually, to find out preferred ratio of components.
Figure 13 is the table at characteristic element, resistivity, opening pond experimental result and peak value angle of wherein listing the ratio of components of sample 1-11 (sample 1-3 as shown in Figure 4).The ratio of components of other materials (sample 4-11) is different mutually in above-mentioned experiment according to inventor's experience.
In 11 kinds of materials, sample 7,10 and 11 is not tested by the pulse tolerance.Because they can not stand 100,000,000 subpulse, be not suitable as the heating resistor of temperature-sensitive ink-jet printer.In the material that does not have by experiment, the mol% of some characteristic elements such as O, the mol% of N and Si/Ta have very big or very little value (drawing the fork branch in the table) than the other materials by the experiment of pulse tolerance.
As the preferred value scope of the advantageous feature of heating resistor according to following definite by the material of the experiment of pulse tolerance and other experiments.The mol% of O (M1) is 25mol%≤M1≤45mol%, and the mol% of N (M2) is 5mol%≤M2≤25mol%, and the mol ratio of Si/Ta is 0.35＜Si/Ta＜0.80.
Figure 14 is the figure that makes according to the figure shown in Fig. 7 (relation between peak value angle and the resistivity), but has also shown the feature result of sample 4-11.In the figure, stain representative is by the result of the material of pulse tolerance experiment, and the result of the material that the white point representative is not tested by the pulse tolerance.
Above-mentioned Fig. 5 of relating to and 7 description show, the zone that resistivity limited that is equal to or less than the peak value angles of 37.5 degree and is equal to, or greater than 4m Ω cm is preferred for heating resistor.But Figure 14 shows that all Ta-Si-O-N materials (sample 1-11) are all in this scope.That is to say, even the sample 4,10 and 11 not by pulse tolerance experiment is also in this scope.Therefore, the suggested scope of preferred material is unaccommodated for the durability of assessing the heating resistor in the temperature-sensitive ink-jet printer such as cavitation resistance etc.
The resistivity of Ta-Si-O-N heater resistor films can change the time.These change in resistance might exert an influence to reliability of products and the design of using this heating resistor.But if the Ta-Si-O-N that makes by sputter, according to annealing can the steady resistance characteristic experiment of (as resistivity, the resistivity rate of change that is heated), this has been known.
Therefore, annealing is the important step of making stable Ta-Si-O-N resistor films.Below detailed description is used for forming by annealing the method for Ta-Si-O-N heater resistor films.
Carry out sputter by sputter equipment under the following conditions.Target: the Ta plate, it comprise scheduled volume Si (Ta: Si=3 for example: 1), pressure: be equal to or less than 1.33 * 10
-4Pa, process gas: the Ar of scheduled volume, base reservoir temperature: about 200 ℃, and layer formation rate: about 2nm/sec.
Forming thickness in the Si substrate is the Ta-Si-O-N film of 480nm, and described substrate is carried out thermal oxide by above-mentioned sputter.As mentioned above, the material of Xing Chenging has impalpable structure thus, and this confirms by X-ray diffraction.If do not anneal, material will have the resistivity that changes in time.
Figure 15 is the figure that shows the changing features between annealed film and the non-annealed film.The material that is used for comparison is the sample 4 shown in Figure 13, and its ratio of components is: 42.0% Ta, 16.0% Si, 30.0% O, and 12.0% N.In the case, under 400 ℃, in atmosphere, anneal.
The transverse axis of this figure is represented the logarithm of time, and with the long time of expression, and vertical pivot is represented change in resistance.Change in resistance on the vertical pivot is relative variation.In the case, 100 represent the initial electrical resistivity (being in 1 place on log scale, should be readily appreciated that) after layer has just formed, and it is as the reference value.In the figure, the result of the non-annealed material of bullet (line " h ") representative, and black point (line " g ") is represented the result of annealed material.
Shown in line " h ", the resistivity of non-annealed material increases in time.On the contrary, the resistivity of annealed material is because annealing increases 20-30%, but with the passing of time, line " g " shows constant resistivity.
The resistance annealing film further carries out the Auger testing electronic microscope, to find oxide-film or oxygen distribution.This test shows, annealing does not produce oxide-film or oxygen distribution, and this is because only find the natural oxide film of 3-5nm thick (it is 0.1% of thickness) in whole test.The reason that resistivity increased when this fact was pointed out out annealing is not because oxidation reaction.
Be the feature difference between investigation annealed film and the non-annealed film, in the opening pond, carry out pressure and increase experiment (SST).The used material of SST is almost with under formation sample 4 the same terms shown in Figure 13 to form.
Figure 16 is the figure that shows the SST result of annealing and non-annealed material.The energy (μ J) of the pulse (2 μ sec pulses during 10kHz) that the transverse axis representative of this figure is applied, and its vertical pivot is represented the rate of change (%) of resistivity.In the case, the thickness of annealed film is 360nm, but not the thickness of annealed film is 700nm.Annealed film and non-annealed film all are 25 square microns.In the figure, the bullet in the line " i " is represented the result of annealed film, and the result of the non-annealed film of the representative of the black point in the line " j ".
The energy range of the pulse that applies is set in about 1.2-5 μ J.1.2 μ J forms the needed floor level of bubble of releasing ink droplet, and 5 μ J are points that material (heater resistor films) is faded, and that is to say that film no longer can proof pressure.Initial electrical resistivity is set at the reference resistance rate that shows the change in resistance rate.Thick more film is strong more usually, and other condition is identical.But thick more non-annealed film is faded at material and is a little shown bigger change in resistance rate.
Scope between dotted line k and the m (2 μ J-3 μ J) is represented the actual range of ink-jet.In this scope, the resistivity range of variation of annealed material (line " i ") is stable, but not the resistivity range of variation of annealed material (line " j ") unstable (once descended, and slightly increased then).
According to shown in Figure 15 over time and the result during practical application, be a very effective factor to the formed Ta-Si-O-N film film that has stability for generation of annealing.
Above-mentioned annealing heater resistor films forms by following steps.Carry out sputter (target: comprise the Ta plate of Si, vacuum pressure: smaller or equal to 1.33 * 10
-4Pa, base reservoir temperature: 200 ℃, process gas: Ar, layer formation rate: 2nm/sec), form electrode layer, form the pattern of electrode layer and heating resistor, then to heating resistor anneal (under 400 ℃, in atmosphere, carrying out 10 minutes).
Be used for driving the double-decker (not shown) that has W-Ti film and Au film according to the electrode of the heating resistor of above-mentioned embodiment of the present invention at Fig. 3.Because electrode layer is formed on the heater resistor films, so electrode layer should contact heater resistor films well.But the Au film that is suitable for electrode layer is difficult to be bonded on the Ta-Si-O-N.The W-Ti film of electrode layer is as basement membrane, and to connect Au film and resistor films, this is Au and Ta-Si-O-N because the W-Ti film can bond well.
During in the state of ink, the electrolysis that short circuit current caused might take place in ink, because ink is a weak electrolyte in electrodes exposed.Electrolysis might form the additional bubbles that the blocking-up ink flows.
For avoiding electrolysis, electrode is answered coating coating insulating film.Oxide insulating film such as Ta-Si-O are preferred.
Figure 17 is the figure that shows according to the insulating film structure of another embodiment of the invention.In this embodiment, also coating coating insulating film of the thermal treatment zone 13 of heating resistor 12.As mentioned above, do not have the Ta-Si-O-N heater resistor films of diaphragm to have excellent cavitation resistance, but coating structure as described in Figure 17 is preferred for the situation of higher cavitation resistance of needs rather than higher energy efficiency.
As shown in figure 17, the thermal treatment zone 13 as shown in Figure 3, single electrode 14 and ordinary electrode 15 all are coated with the diaphragm 21 that Ta-Si-O makes.Figure 18 A-18C is a sectional view of explaining the method for formation heater element as shown in figure 17 length by length.Figure 18 A-18C has at length shown the structure of electrode (single electrode 14 and ordinary electrode 15).
Shown in Figure 18 B, electrode has three-decker, comprising the following adhesive film 22 of W-Ti, the electrode film 23 of Au and the last adhesive film 24 of W-Ti.The electrode of these structures and the thermal treatment zone 13 are coated with the insulating protective film 21 that the Ta-Si-O material is made, and this film insulation has excellent cavitation resistance.
Last tack coat 24 be used to bond Au and Ta-Si-O connect Au electrode film 23 and Ta-Si-O diaphragm 21 thus securely.Therefore, heater element and ink separate.
The step that forms these heater elements that are formed with insulating protective film thereon will be described in detail with reference to figure 18A-18C.
At first, adhesive film 22, electrode film 23 and last adhesive film 24 (Figure 18 A) under deposition on the heater resistor films 12 that is deposited on the substrate 11.Then, form the pattern of adhesive film 22, electrode film 23 and last adhesive film 24 down, to form the thermal treatment zone 13, single electrode 14 and ordinary electrode 15 (Figure 18 B).Then form the pattern of heater resistor films 12, to form heater element.
Following step should be annealing, but in atmosphere, heater resistor films 12 annealed and make simultaneously W-Ti on adhesive film 24 contact with electrode film 23, understand on last adhesive film 24, producing oxide layer.More precisely, airborne oxygen under these conditions during annealing because high temperature becomes free atom.The surface of adhesive film 24 in the free atom oxidation.Because the oxide layer that is difficult to form thus is bonded on the Ta-Si-O diaphragm 21,, W-Ti can not play the effect that connects diaphragm 21 and electrode film 23 so going up adhesive film 24.
Be used to the condition of annealing below the setting, to avoid the formation of oxide layer.
At first in inert gas, anneal, to avoid the formation of free oxygen.Inert gas is a generic name of representing hypoergia gas, as the 0 element He of family, Ar, Kr, Xe and Rn (rare gas), and N
2Gas.In this embodiment, use N
2Gas and Ar gas.
Step and concrete condition are as follows.
(1) forms the Ta-Si-O-N heater resistor films.
(2) form adhesive film (W-Ti) down.
(3) form electrode film (Au).
(4) adhesive film (W-Ti) in the formation.
(5) electrode layer (W-Ti, Au, W-Ti) is formed pattern.
(6) heater resistor films is formed pattern.
(7) heater resistor films is annealed.
Atmosphere: N
2Gas (inert gas)
Temperature: 350-450 ℃
Processing time: 10-30 minute
(8) form oxide insulating film (Ta-Si-O).
(9) oxide insulating film (Ta-Si-O) is formed pattern.
According to said method, last adhesive film 24 is not oxidized, and this is because at N
2Anneal in the gas.
Because the last adhesive film of W-Ti 24 is not oxidized, thus on last adhesive film 24, form Ta-Si-O oxide insulating film 21 securely, and realize the firm connection between Ta-Si-O dielectric film 21 and the Au electrode film 23 thus.
When in Ar gas, annealing, can use identical step.
Another kind method is to anneal in vacuum chamber.In the case, this vacuum chamber is the sputtering chamber that is used for sputter, and therefore annealing is carried out after forming heating resistor by sputter continuously.Annealing in vacuum chamber realizes by radiant heat.Said method prevents upward adhesive film 24 of free oxygen contact.
Annealing can be carried out after forming the Ta-Si-O oxide insulating film, goes up adhesive film 24 to prevent the free oxygen contact.In the case, annealing can be carried out in atmosphere (air).
Step and condition that this method is used are as follows.
(1) forms the Ta-Si-O-N heater resistor films.
(2) form adhesive film (W-Ti) down.
(3) form electrode film (Au).
(4) adhesive film (W-Ti) in the formation.
(5) electrode layer (W-Ti, Au, W-Ti) is formed pattern.
(6) heater resistor films is formed pattern.
(7) form oxide insulating film (Ta-Si-O).
(8) oxide insulating film (Ta-Si-O) is formed pattern.
(9) heater resistor films is annealed.
Atmosphere: air (atmosphere)
Temperature: 350-450 ℃
Processing time: 10-30 minute
Figure 19 is the figure that shows the resistivity increment rate of heater resistor films, and this heater resistor films is annealed, still at different atmospheric conditions: atmosphere (air) (representing with black circle), N
2Gas (representing), Ar gas (representing) with white triangle with black triangle, form the Ta-Si-O oxide insulating film and form pattern after with air (hereinafter referred to as " and use air when having diaphragm) (representing) with cross wires.The transverse axis of this figure represent annealing temperature (℃), and vertical pivot is represented the sheet resistivity increment rate of heater resistor films.In the case, the processing time of annealing is 10 minutes.
As shown in figure 19, in 200-400 ℃ temperature range, no matter atmospheric condition how, the increment rate of sheet resistivity is linear to be increased.Then, after temperature surpassed 400 ℃, increment rate slowly descended.Even increment rate descends, resistivity itself is still increasing continuously.This result shows that the resistivity stabilization that annealing produces only depends on heat, rather than atmospheric condition.
When being used for the temperature-sensitive ink-jet printer, heating resistor should be annealed under at least 350 ℃, and this is to be equal to, or greater than 300 ℃ heat because heating resistor discharges when being driven in printer.In other words, if resistor is to anneal being equal to or less than under 300 ℃ the temperature, then the effect that produces of annealing does not show.When temperature was lower than or be higher than 400 ℃, annealing temperature was high more, and the change in resistance rate is then more little.Figure 19 can reflect this fact significantly.In the figure, when temperature equaled or be higher than 400 ℃, it is more and more littler that increment rate becomes.But the known annealing temperature that surpasses 600 ℃ is also damaged cavitation resistance.In the monolithic type structure, heating resistor and drive circuit thereof are installed on the identical silicon base, and then Zui Da annealing temperature is defined as 450 ℃, and this is because " 400 ℃ 1 hour " are the limit values of the diffusion layer of LSI on the silicon base.Therefore, should be to the annealing region of the heating resistor that is used for monolithic type temperature-sensitive ink-jet printer at 350-450 ℃.
Figure 20 is the figure that is presented at the relation between the relative resistance rate of annealing time and resistance annealing film under the different atmosphere condition identical with condition shown in Figure 19, the transverse axis of this figure represent annealing time (minute), and vertical pivot is represented the relative resistance rate, wherein 100 expression initial electrical resistivity.In the case, annealing temperature is 400 ℃.
As shown in figure 20, no matter atmospheric condition how, during begin to anneal 4 minutes, resistivity sharply increases.Then, resistivity slowly increased, until the 10th minute.In 10 minutes-30 minutes time, resistivity is stable.
Therefore, the preferred process time of annealing is 10-30 minute.In other words, lower bound should be set in 10 minutes, and wherein the rapid increase of resistivity stops, and high limit should be set in 30 minutes, and wherein resistivity is stable.
As mentioned above, the resistivity of Ta-Si-O-N heater resistor films is stablized by annealing.The effect that annealing is produced does not depend on the difference of atmosphere.In addition, even the effect of annealing does not change when heater element is capped yet.This fact makes heater element can have protective layer thereon, with the high reliability printhead of preparation temperature-sensitive ink-jet printer.In the case, annealing should be carried out in inert gas or after forming diaphragm, and is oxidized to prevent the tack coat between heater element and the protective layer, and diaphragm is bonded on the heater element securely.
Under the situation that does not break away from the spirit and scope of the present invention, various embodiments also can be arranged and carry out various improvement.
For example, heating resistor of the present invention is not only made by Ta, Si, O and N, also can comprise other elements, as hydrogen etc.
Heating resistor of the present invention does not limit to and is used for the temperature-sensitive ink-jet printer.Heating resistor of the present invention also can be used for for example using the ink-jet printer of piezo-electric effect, perhaps any product except that ink-jet printer.
Above-mentioned embodiment only is to be used to illustrate the present invention, rather than limitation of the scope of the invention.Scope of the present invention is shown in appended claims, rather than above-mentioned embodiment.In being equal in the replacement of claims of the present invention, also can carrying out various improvement, and in claims, should be regarded as within the scope of the present invention.
The application is based on H11-133306 number and the 2000-67612 Japanese patent application of submitting on May 13rd, 1999 of submitting on March 10th, 2000, and comprises specification, claims, accompanying drawing and summary.The content of above-mentioned Japanese patent application is incorporated herein by reference at this.
Claims (12)
1, a kind of heating resistor that is used for the printhead of ink-jet printer, this resistor sends heat energy when applying electric current, and produces bubble when the contact ink,
Described heating resistor (12) comprises that Ta, Si, O and N are as component at least, and wherein the mol% of N is M2, and the span of M2 is 5mol%≤M2≤25mol%.
2, heating resistor as claimed in claim 1, wherein, the mol of Si/Ta ratio is 0.35＜Si/Ta＜0.80.
3, heating resistor as claimed in claim 2, wherein, the mol% of O is M1, the span of M1 is 25mol%≤M1≤45mol%.
4, heating resistor as claimed in claim 1, wherein, the mol% of O is M1, the span of M1 is 25mol%≤M1≤45mol%.
5, heating resistor as claimed in claim 1, wherein, described heating resistor (12) directly contacts ink.
6, make the method for the heating resistor of claim 1, this heating resistor (12) is used for the printhead of temperature-sensitive ink-jet printer, said method comprising the steps of:
Go up the film that formation is made by Ta-Si-O-N in substrate (11), this film comprises that Ta, Si, O and N are as component at least, and wherein the mol% of N is M2, and the span of M2 is 5mol%≤M2≤25mol%; And
By forming heating resistor (12) at the described Ta-Si-O-N film of 350-600 ℃ annealing temperature.
7, method as claimed in claim 6, wherein, annealing is to carry out in air.
8, method as claimed in claim 6, wherein, annealing is to carry out in inert gas.
9, method as claimed in claim 6, wherein, the described printhead of temperature-sensitive ink-jet printer is the printhead of monolithic type, wherein printhead is installed on the identical silicon base with drive circuit, and annealing during temperature 350-450 ℃.
10, method as claimed in claim 6, wherein, annealing was carried out 10-30 minute.
11, method as claimed in claim 6, wherein, described Ta-Si-O-N film has diaphragm (21) thereon.
12, method as claimed in claim 11, wherein, described annealing is to carry out in air.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP133306/1999 | 1999-05-13 | ||
| JP13330699 | 1999-05-13 | ||
| JP67612/2000 | 2000-03-10 | ||
| JP2000067612 | 2000-03-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1304362A CN1304362A (en) | 2001-07-18 |
| CN1201933C true CN1201933C (en) | 2005-05-18 |
Family
ID=26467693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00800849 Expired - Fee Related CN1201933C (en) | 1999-05-13 | 2000-05-09 | Heating resistor and manufacturing method thereof |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1098770A1 (en) |
| CN (1) | CN1201933C (en) |
| WO (1) | WO2000069635A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005205889A (en) * | 2003-12-26 | 2005-08-04 | Canon Inc | Inkjet recording head manufacturing method and inkjet recording head manufactured by the method |
| JP6066786B2 (en) * | 2013-03-14 | 2017-01-25 | キヤノン株式会社 | Liquid discharge head, recording apparatus, liquid discharge head manufacturing method, liquid discharge head substrate, and liquid discharge head substrate manufacturing method |
| WO2017222551A1 (en) | 2016-06-24 | 2017-12-28 | Hewlett-Packard Development Company, L.P. | Amorphous thin metal film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4591821A (en) * | 1981-06-30 | 1986-05-27 | Motorola, Inc. | Chromium-silicon-nitrogen thin film resistor and apparatus |
| JPS60259469A (en) * | 1984-06-05 | 1985-12-21 | Alps Electric Co Ltd | Thermal head |
| JPS61172754A (en) * | 1985-01-26 | 1986-08-04 | Kyocera Corp | Thermal head |
| JPH0733091B2 (en) * | 1990-03-15 | 1995-04-12 | 日本電気株式会社 | INKJET RECORDING METHOD AND INKJET HEAD USING THE SAME |
| JP3194465B2 (en) * | 1995-12-27 | 2001-07-30 | 富士写真フイルム株式会社 | Inkjet recording head |
| US6527813B1 (en) * | 1996-08-22 | 2003-03-04 | Canon Kabushiki Kaisha | Ink jet head substrate, an ink jet head, an ink jet apparatus, and a method for manufacturing an ink jet recording head |
| ES2201231T3 (en) * | 1996-08-22 | 2004-03-16 | Canon Kabushiki Kaisha | SUBSTRATE FOR PRINT HEAD BY INK JETS, METHOD FOR MANUFACTURING OF THE SAME, PRINT HEAD FOR INK JETS GIVEN WITH SUCH SUBSTRATE, AND METHOD FOR MANUFACTURE OF SUCH HEAD. |
-
2000
- 2000-05-09 EP EP00922999A patent/EP1098770A1/en not_active Withdrawn
- 2000-05-09 CN CN 00800849 patent/CN1201933C/en not_active Expired - Fee Related
- 2000-05-09 WO PCT/JP2000/002950 patent/WO2000069635A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1098770A1 (en) | 2001-05-16 |
| WO2000069635A1 (en) | 2000-11-23 |
| CN1304362A (en) | 2001-07-18 |
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