CN1294098C - Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof - Google Patents
Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof Download PDFInfo
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- CN1294098C CN1294098C CNB2005100498287A CN200510049828A CN1294098C CN 1294098 C CN1294098 C CN 1294098C CN B2005100498287 A CNB2005100498287 A CN B2005100498287A CN 200510049828 A CN200510049828 A CN 200510049828A CN 1294098 C CN1294098 C CN 1294098C
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Abstract
The present invention discloses titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure, and a preparation method for the titanium silicide coated glass. A layer of film is deposited on a common float glass base plate, or a layer of silicon film is deposited between the film and the common float glass base plate. A composite film of titanium silicide or silicon is obtained through preparation, or a composite film composed of titanium silicide and silicon carbide, or composed of titanium silicide and titanium carbide, or composed of titanium silicide and silicon nitride, or composed of titanium silicide and titanium nitride is obtained by adding a small amount of active carbon or nitrogen into the film, so that the mechanical strength and the chemical corrosion resisting capability of the coated glass are enhanced. The present invention is novel coated glass which integrates a light adjusting function, a heat insulating function and a low emissivity glass function into a whole.
Description
Technical field
The present invention relates to the technology of preparing of titanium silicide film coating glass, refer more particularly to normal pressure thermolysis chemical gaseous phase depositing process, nitrogen protection, online formation high-performance silication titanium coated glass and preparation method thereof.
Background technology
With the raising of modern life quality, people are more and more higher to the requirement of amenity in the holding chamber and protection privacy, so coated glass arises at the historic moment.At present, the coated glass as the building glass curtain wall mainly contains two kinds: a kind of is the heat insulation coated glass of light modulation, and another kind is a low radiation coated glass.
The heat insulation coated glass of light modulation is mainly used in to be controlled in sunlight and the heat inlet chamber summer.Known solar radiation spectrographic wavelength is between 300～3000nm, being distributed as of the total heat that radiated electromagnetic wave enters by window: the ultraviolet region less than 425nm is about 15%, 425～675nm visible range is about 40%, and the district is about 45% at 675～1200nm wavelength region near infrared (NIR).As seen, the near infrared (NIR) of 675～1200nm wavelength region district have nearly half solar radiation energy with inlet chamber in, thereby as excellent light modulation heat insulation (Solarcontrol) glass, on the one hand the ability that stops visible light transmissive in 425～675nm scope preferably should be arranged, preferably NIR be had high-reflectivity on the other hand.At present, the general film that reflects and absorb two kinds of patterns that uses reaches control sunlight and the interior purpose of heat inlet chamber.
Low radiation coated glass is mainly used in winter, when sunlight sees through well, can reflect the mid and far infrared line that indoor object emission is arranged well, reduces thermal losses, thereby reaches energy-conservation effect.Low radiation coated glass is divided into two big classes: a kind of is dielectric medium-metal-dielectric medium composite film, and another kind is a transparent conductive film, as highly doped wide bandgap semiconductor.They mainly are to reach different reflectivity and specific absorption to the electromagnetic radiation of different frequency by the carrier concentration (reducing the resistivity of film) of regulating in the film, thereby realize seeing through and the far reflection of centering visible light.
People focus on exploitation to attention to have the composite film coating of light modulation thermal insulation film and low radiation film function simultaneously on glass in recent years.In fact this glass can both play energy-conservation effect in summer and winter, summer composite film coating glass when block sunlight sees through well, can stop again in the heat inlet chamber of outdoor high temperature object radiation and reflection, reduce room conditioning energy expenditure in summer; Then can reflect mid and far infrared line in the winter time well, reduce thermal losses by indoor object emission.At present, generally can make multilayer complex films and realize the compound of these two kinds of functions by light modulation thermal isolation film and low-radiation film MULTILAYER COMPOSITE.Titanium silicide (TiSi
2) film is a kind of film that had not only had shielding sunlight but also had reflection mid and far infrared radiative property, so TiSi
2Coated glass can integrate sunlight control and low radiation functions, can make a kind of novel coated glass with this.TiSi
2Two kinds of crystal phase structures are arranged: a kind of is the end-centered orthorhombic structure; Unit cell dimension is: a=0.362nm, b=1.376nm, c=0.360nm; Electricalresistivity=60～100 μ Ω-cm; Another kind is the face-centered orthorhombic structure, and unit cell dimension is: a=0.826nm, b=0.480nm, c=0.853nm; Resistivity is ρ=12～20 μ Ω-cm, and fusing point is 1540 ℃.The end-centered orthorhombic structure changes the face-centered orthorhombic structure into when being higher than 750 ℃.The TiSi of face-centered orthorhombic structure
2Film has very low resistivity, therefore low-frequency electromagnetic wave is had very high reflectivity, can shield a large amount of solar thermal energies; And TiSi
2Film has approximately identical transmitance at whole visible region, has neutralc tint, and observing scene is undistorted, thereby this film has special importance for using on window glass.
The preparation method of existing coated glass can be divided into two big classes: a kind of is off-line coated method, as vacuum-evaporation, d.c. sputtering, radio-frequency sputtering, magnetron sputtering, ion beam sputtering and ion plating etc., this method is that the finished glass that will continuously produce on the glass production line utilizes various film coating method to carry out plated film (claiming off-line coated) after cutting again; Another kind is an on-line film coating method, as chemical vapor deposition (CVD) and spraying technology, directly carries out plated film (title on-line coating) in this method on glass float glass process production line.Vacuum-evaporation only is used for low melting point, heats volatile material, and film forming material is restricted, and quality of coating is not good enough, and needs operation under vacuum, can only be off-line coated; Sputtering method can obtain the film of better quality, but sedimentation velocity is slow, apparatus expensive, and complicated operation, cost height can only be off-line coated; The spraying technology sedimentation velocity is fast, but the sprayed coating lack of homogeneity; CVD is fabulous coating process, and quality of forming film is higher.Use more have APCVD (atmospheric pressure cvd), LPCVD (low pressure chemical vapor deposition), PECVD (plasma enhanced CVD), LICVD (induced with laser CVD) etc. in the CVD technology.Low pressure chemical vapor deposition can improve the homogeneity of film, and the quality of film is better, but cost is higher, the equipment complexity, and sedimentation velocity reduces, and is difficult for realizing on-line coating; PECVD, LICVD are similar, can reduce depositing temperature, improve the homogeneity of film, but the cost height, technology and equipment complexity, unsuitable on-line coating; Atmospheric pressure cvd has big sedimentation velocity, and operation under atmospheric pressure, belong to normal pressure technology, be easy to realize the continuous coating of online or off-line, be suitable for large-area coating film, production cost is low, device simple, particularly directly utilize the heat energy in the glass production, saved the energy greatly, but and the flexible tempering of coated glass of preparation.
Because the society and the economic implications in coated glass field, the research of coated glass has at present now become focus both domestic and external, for example BFG glass group, Libbey-Owens-Ford company, Pilkington brother company limited, PPG Industries Inc., American Glass Research limited-liability company, M﹠amp; Transnational companys such as T chemistry limited-liability company apply for relevant coated glass patent right, dog-eat-dog in China after 1985 in succession.Off-line coated technical elements, Shenzhen south BJ Glass Group Co., Luoyang BJ Glass Group Co., Shanghai the shine magnificent glass company etc. of magnificent BJ Glass Group Co., Qinhuangdao that shines successively introduces vacuum magnetic-control sputtering filming equipment, hundreds thousand of square metres approximately of the throughput years of every complete equipment with huge fund (as to U.S. AIRCO company) since 1985.The on-line coating process aspect, because of reasons such as its throughput are big, and cost is low, with the obvious advantage in competition.By silicomethane thermolysis in nonoxidizing atmosphere formation polysilicon, the Nano thin film technology of Qinhuangdao Glass Inst.'s exploitation, on the glass float glass line, realize the production of serialization, belong to a domestic technology of success.This technology is mainly used to prepare various sunlight control energy-saving glass, and present Weihai blue star a company produces energy-conservation coated glass per year and just reaches nearly 10,000,000 square metres.On the other hand, at present, the Qinhuangdao magnificent glass company that shines has introduced low radiation coated glass online production technology, blue star company of Zhejiang University also independent development low radiation coated glass online production technology, begun the online preparation of simple low radiation functions glass at home.
TiSi
2Film has shielding sunlight and reflection mid and far infrared radiating complex function characteristic.Gordon has applied for relevant TiSi
2The patent US5167986 of coated glass and WO89/10209, but patent has only been introduced TiSi
2Coated glass is as the application and the online preparation of light modulation heat-protecting glass.Gordon adopts SiH
4-TiCl
4-He system forms TiSi at 650～680 ℃ on glass substrate
2Film, TiSi
2Film has neutralc tint and higher near infrared reflectivity.Patent is not pointed out the TiSi that generated
2The structure of film and resistivity, and this is to infrared reflectance, the special far reflectivity of centering has very important influence, and promptly this patent does not obtain the TiSi that the centering far infrared rays has high-reflectivity yet
2Film does not also promptly obtain to hang down the TiSi of radiation characteristic with this
2Coated glass.Gordon uses helium as the inert protective gas of reacting in addition; but the inert protective gas in the molten tin bath on actual float glass process on-line coating glass production line is a nitrogen; these are different with industrial practical situation, and will improve production cost with helium greatly as the inert protective gas of reacting.In the present invention, from combining, reduce production costs with actual production and from good low radiation characteristic angle, development and use nitrogen is as inert protective gas, and is identical with inert protective gas in the molten tin bath, and with this as TiCl
4Carrier gas, moreover, in reaction process, utilize the minor N atom to enter to form in the crystalline structure interstitial solid solution, form the compound of silicon etc., thereby reach TiSi
2The modification of film improves the wear resistance and the chemical resistance of film, particularly preparation low-resistivity film and obtain high mid and far infrared reflectivity coated glass and success as purposes such as high-performance low emissivity glass uses on glass substrate successfully.Clearly, the nitrogen protection of atmospheric pressure cvd method prepares titanium silicide film coating glass and has than with the more obvious advantage of helium protection preparation with obtain low radiation/sunlight control complex function novel high-performance coated glass.
In view of this invention purpose is with the low radiation of the online quick and large-area nitrogen protection industrial-scale production of chemical vapor deposition (CVD) process implementing/sunlight control complex function titanium silicide film coating glass; reactant must be easily gasification, because could obtain big mass transfer ability under big vapour pressure.When determining technological line, also must consider the transmission speed of glass production 5-15m/min, glass molten tin bath temperature is primary condition such as 600-1000 ℃, the sedimentation velocity and the crystalline phase formation condition of design film should adapt with it, and consider that will there be big bond strength at film and glass substrate interface, and the source of raw material, cost, production control and environmental pollution control etc. are all multifactor.SiH involved in the present invention
4-TiCl
4-N
2Atmospheric pressure cvd can meet above-mentioned requirements fully as the basic technology route.
Summary of the invention
The object of the present invention is to provide a kind of nitrogen protection to prepare the method and the titanium silicide film coating glass of titanium silicide film coating glass.
The technical scheme that the present invention solves its technical problem employing is as follows:
One, the titanium silicide film coating glass of nitrogen protection preparation:
On common float-glass substrate, deposit thin film, or between common float-glass substrate and film, deposit one deck silicon film again.
Described film is titanium silicide, titanium silicide composite S i, titanium silicide composite SiC or titanium silicide composite S i
3N
4
Titanium silicide in the described film is the face-centered orthorhombic crystal structure, and the square resistance of film is 1～100 Ω/.
Two, nitrogen protection under normal pressure prepares the preparation method of complex function titanium silicide film coating glass, and the step of this method is as follows:
1) reactant is SiH
4And TiCl
4, in the reaction chamber when off-line prepares with N
2Or in the molten tin bath in online when preparation with N
2, H
2Mixed gas is diluent gas and protective atmosphere;
2) SiH
4, TiCl
4And N
2Mix at mixing chamber; Each road gas equates that at the pressure of mixing chamber ingress pressure remains between 111325～131325Pa;
3) TiCl
4Constant temperature is at 30～70 ℃; TiCl
4Pipeline heat insulation to 40～80 ℃ of process;
4) by producer gas generator, use N
2Carry TiCl
4
5) SiH
4, TiCl
4And N
2Obtain reactant gases in the mixing chamber mixing;
6) volumetric molar concentration of each material in the reactant gases:
a)SiH
4：1～25％；
b)TiCl
4：0.1～10％；
C) SiH
4/ TiCl
4Mol ratio: 1～10;
D) N
2Or N
2, H
2Mixed gas: 50%～99%;
7) depositing system pressure is between 101325～131325Pa;
8) the glass substrate temperature is between 650～750 ℃, and reactant gases is transported on the glass substrate and reacts, and generates TiSi
2Film, growth for Thin Film speed are 10～50 nm/sec, and depositing time is 1～15 second;
9) waste gas is handled the back discharging through absorbing.
The ethene or the methane that add 1～20% volumetric molar concentration in reactant gases form TiSi
2Composite SiC or TiSi
2The film of composite Ti C, the wear resistance and the chemical resistance of film further improve.
The ammonia that adds 1～30% volumetric molar concentration in reactant gases forms TiSi
2Composite S i
3N
4Or TiSi
2The film of composite Ti N, the wear resistance and the chemical resistance of film further improve.
The present invention compares the useful effect that has with background technology:
1, uses nitrogen as inert protective gas, realize online low cost production titanium silicide film coating glass;
2, use nitrogen as inert protective gas, realize online low cost production titanium silicide film coating glass;
3, obtain the TiSi of low-resistance face-centered orthorhombic crystal formation
2Coated glass, its centering far-infrared radiation has very high reflectivity;
4, the titanium silicide film coating glass that obtains has shielding effect to sunlight, and reflected light and transmitted light all are neutralc tint simultaneously.Transmission is light gray, is reflected into silver color;
5, to the titanium silicide film coating glass modification, mixing has active carbon or nitrogen on a small quantity, improves the wear resistance and the chemical resistance of this coated glass, increases the work-ing life of this coated glass;
6, to the titanium silicide film coating glass modification, add excessive silicon, improve the firmness that combines of film and glass;
7, obtained low-resistance TiSi
2Film has very high reflectivity to mid and far infrared.Reflection and transmission to sunlight simultaneously all is neutralc tint, eliminated and dazzled the light interference;
8, use nitrogen as inert protective gas; replace Gordon and in U.S. Pat 5167986 and WO89/10209, use the inert protective gas of helium as reaction; greatly reduce production cost; and the minor N atom also can enter and forms interstitial solid solution in the crystalline structure in reaction process, thereby reach TiSi
2The modification of film, the wear resistance and the chemical resistance of raising film.
Description of drawings
Fig. 1 is the double-layer structure synoptic diagram of coated glass of the present invention;
Fig. 2 is the three-decker synoptic diagram of coated glass of the present invention.
Embodiment
As shown in Figure 1 and Figure 2, deposition thin film 1 on common float-glass substrate 2, or between common float-glass substrate 2 and film 1, deposit one deck silicon film 3 again.
Described film 1 is titanium silicide, titanium silicide composite S i, titanium silicide composite SiC or titanium silicide composite S i
3N
4
Titanium silicide in the described film 1 is the face-centered orthorhombic crystal structure, and the square resistance of film 1 is 1～100 Ω/.
Be embodiments of the invention below:
Embodiment one
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 60 ℃, TiCl
4The pipeline heat insulation to 70 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 2, SiH
4: 10%, TiCl
4: 5%, N
2: 85%, the pressure of each road gas in the mixing chamber ingress is 121325Pa, depositing system pressure maintains 105000Pa, about 10 seconds of depositing time.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment two
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 6, SiH
4: 6%, TiCl
4: 1%, N
2: 93%, the pressure of each road gas in the mixing chamber ingress is 121325Pa, depositing system pressure maintains 105000Pa, about 10 seconds of depositing time.On glass substrate, form TiSi
2With the Si laminated film.The results are shown in subordinate list.
Embodiment three
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 35 ℃, TiCl
4The pipeline heat insulation to 45 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 10, SiH
4: 20%, TiCl
4: 2%, N
2: 78%, the pressure of each road gas in the mixing chamber ingress is 121325Pa, depositing system pressure maintains 105000Pa, about 10 seconds of depositing time.On glass substrate, form TiSi
2With the Si laminated film.The results are shown in subordinate list.
Embodiment four
650 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 9%, TiCl
4: 3%, N
2: 88%, the pressure of each road gas in the mixing chamber ingress is 121325Pa, depositing system pressure maintains 105000Pa, about 10 seconds of depositing time.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment five
750 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, N
2: 98%, the pressure of each road gas in the mixing chamber ingress is 121325Pa, depositing system pressure maintains 105000Pa, about 10 seconds of depositing time.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment six
700 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, N
2: 98%, about 10 seconds of depositing time, the pressure of each road gas in the mixing chamber ingress is 111325Pa, depositing system pressure maintains 111325Pa.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment seven
700 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, N
2: 98%, about 10 seconds of depositing time, the pressure of each road gas in the mixing chamber ingress is 131325Pa, depositing system pressure maintains 121325Pa.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment eight
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, N
2: 98%, the pressure of each road gas in the mixing chamber ingress is 131325Pa, depositing system pressure maintains 121325Pa, depositing time 5 seconds.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment nine
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, N
2: 98%, the pressure of each road gas in the mixing chamber ingress is 131325Pa, depositing system pressure maintains 121325Pa, depositing time 15 seconds.On glass substrate, form TiSi
2Film.The results are shown in subordinate list.
Embodiment ten
700 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, mix 10% NH
3, N
2: 88%, depositing system pressure maintains 121325Pa, depositing time 10 seconds.On glass substrate, form TiSi
2/ Si
3N
4Laminated film.The results are shown in subordinate list.
Embodiment 11
700 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, mix 10% C
2H
4, N
2: 88%, depositing system pressure maintains 121325Pa, depositing time 10 seconds.On glass substrate, form TiSi
2/ SiC laminated film.The results are shown in subordinate list.
Embodiment 12
700 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, conditioned reaction gas SiH
4/ TiCl
4Mol ratio is 3, SiH
4: 1.5%, TiCl
4: 0.5%, mix 10% CH
4, N
2: 88%, depositing system pressure maintains 121325Pa, depositing time 10 seconds.On glass substrate, form TiSi
2/ SiC laminated film.The results are shown in subordinate list.
Embodiment 13
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, depositing system pressure maintains 121325Pa, deposition silicon layer 5 seconds on glass substrate earlier, re-adjustment reactant gases SiH
4/ TiCl
4Mol ratio is 2, SiH
4: 5%, TiCl
4: 2.5%, N
2: 97%, depositing Ti Si
2Film 5 seconds.The results are shown in subordinate list.
Embodiment 14
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, depositing system pressure maintains 121325Pa, deposition silicon layer 5 seconds on glass substrate earlier, re-adjustment reactant gases SiH
4/ TiCl
4Mol ratio is 2, SiH
4: 5%, TiCl
4: 2.5%, mix 20% NH
3, N
2: 72.5%, depositing Ti Si
2/ Si
3N
4Composite membrane 5 seconds.The results are shown in subordinate list.
Embodiment 15
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, depositing system pressure maintains 121325Pa, deposition silicon layer 5 seconds on glass substrate earlier, re-adjustment reactant gases SiH
4/ TiCl
4Mol ratio is 2, SiH
4: 5%, TiCl
4: 2.5%, mix 20% C
2H
4, N
2: 72.5%, depositing Ti Si
2/ SiC composite membrane 5 seconds.The results are shown in subordinate list.
Embodiment 16
680 ℃ of depositing temperatures, TiCl
4Constant temperature is at 40 ℃, TiCl
4The pipeline heat insulation to 50 ℃ of process, depositing system pressure maintains 121325Pa, deposition silicon layer 5 seconds on glass substrate earlier, re-adjustment reactant gases SiH
4/ TiCl
4Mol ratio is 2, SiH
4: 5%, TiCl
4: 2.5%, mix 20% CH
4, N
2: 72.5%, depositing Ti Si
2/ SiC composite membrane 5 seconds.The results are shown in subordinate list.
Test result
The sign of subordinate list one film
| Embodiment | Crystalline phase in the film | The atom that exists in the film | Atomic ratio Ti: Si: X in the film | Film thickness | Film rectangular resistance (Ω/) |
| Embodiment one | TiSi 2 | Ti，Si | 1∶1.9 | 300nm | 10 |
| Embodiment two | TiSi 2，Si | Ti，Si | 1∶3 | 200nm | 28 |
| Embodiment three | TiSi 2，Si | Ti，Si | 1∶25 | 260nm | 70 |
| Embodiment four | TiSi 2 | Ti，Si | 1∶2.2 | 150nm | 45 |
| Embodiment five | TiSi 2 | Ti，Si | 1∶2.1 | 240nm | 8 |
| Embodiment six | TiSi 2 | Ti，Si | 1∶2.1 | 170nm | 37 |
| Embodiment seven | TiSi 2 | Ti，Si | 1∶2.1 | 140nm | 58 |
| Embodiment eight | TiSi 2 | Ti，Si | 1∶2.1 | 100nm | 30 |
| Embodiment nine | TiSi 2 | Ti，Si | 1∶2.1 | 300nm | 5 |
| Embodiment ten | TiSi 2，Si 3N 4 | Ti，Si，，N | 1∶1∶1 | 180nm | 15 |
| Embodiment 11 | TiSi 2，SiC | Ti，Si，C | 1∶1.9∶0.05 | 120nm | 30 |
| Embodiment 12 | TiSi 2，SiC | Ti，Si，C | 1∶1.9∶003 | 140nm | 25 |
| Embodiment 13 | TiSi 2，Si | Ti，Si | 1∶4 | 100nm+80nm | 2 |
| Embodiment 14 | TiSi 2，Si，Si 3N 4 | Ti，Si，N | 1∶5∶0.3 | 80nm+80nm | 10 |
| Embodiment 15 | TiSi 2，Si，SiC | Ti，Si，C | 1∶4∶0.06 | 60nm+80nm | 30 |
| Embodiment 16 | TiSi 2，Si，SiC | Ti，Si，C | 1∶4∶0.04 | 70nm+80nm | 25 |
The optical property of subordinate list two films
| Embodiment | Ultraviolet-visible transmitance (T334nm) | Ultraviolet-visible transmitance (T550nm) | Infrared transmittivity (T1500nm) | The mid and far infrared reflectivity |
| Embodiment one | 0.5％ | 15％ | 11％ | 90％ |
| Embodiment two | 0.9％ | 36％ | 25％ | 76％ |
| Embodiment three | 1.7％ | 34％ | 31％ | 53％ |
| Embodiment four | 4％ | 45％ | 34％ | 65％ |
| Embodiment five | 1.3％ | 35％ | 28％ | 92％ |
| Embodiment six | 3％ | 38％ | 31％ | 70％ |
| Embodiment seven | 2％ | 51％ | 40％ | 59％ |
| Embodiment eight | 3％ | 38％ | 31％ | 75％ |
| Embodiment nine | 0.3％ | 15％ | 10％ | 95％ |
| Embodiment ten | 3％ | 19％ | 15％ | 86％ |
| Embodiment 11 | 5％ | 28％ | 19％ | 75％ |
| Embodiment 12 | 5％ | 30％ | 22％ | 78％ |
| Embodiment 13 | 0.2％ | 26％ | 8％ | 98％ |
| Embodiment 14 | 1.5％ | 30％ | 11％ | 90％ |
| Embodiment 15 | 3.8％ | 33％ | 15％ | 75％ |
| Embodiment 16 | 3.4％ | 31％ | 14％ | 78％ |
The chemistry and the mechanical property of subordinate list three films
| Embodiment | Solidity to corrosion | Acid resistance | Alkali resistance | Wear resistance | Coating scratch resistance trace |
| Embodiment one | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment two | There is not corrosion | There is not corrosion | There is not corrosion | ＞35000 times | No scratch |
| Embodiment three | There is not corrosion | There is not corrosion | There is not corrosion | ＞35000 times | No scratch |
| Embodiment four | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment five | There is not corrosion | There is not corrosion | There is not corrosion | ＞35000 times | No scratch |
| Embodiment six | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment seven | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment eight | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment nine | There is not corrosion | There is not corrosion | There is not corrosion | ＞30000 times | No scratch |
| Embodiment ten | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
| Embodiment 11 | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
| Embodiment 12 | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
| Embodiment 13 | There is not corrosion | There is not corrosion | There is not corrosion | ＞35000 times | No scratch |
| Embodiment 14 | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
| Embodiment 15 | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
| Embodiment 16 | There is not corrosion | There is not corrosion | There is not corrosion | ＞40000 times | No scratch |
Crystalline phase is tested with X-ray diffractometer in the film.
Thicknesses of layers is by scanning electron microscope test.
Contained element and ratio thereof are tested by EDX in the film.
The mid and far infrared reflectivity is by formula R
IR=(1+0.0053R
S)
-2Calculate R
IRAnd R
SRepresent the square resistance of mid and far infrared reflectivity and film respectively.
Solidity to corrosion experiment be in the solution of 5%NaCl soaking at room temperature above 5 months.
Acid resistance experiment is to be heated to 60 ℃ to soak 36 hours in pH value is 5 solution.
Alkali resistance experiment is to be heated to 60 ℃ to soak 36 hours in pH value is 9 solution.
The wear resistance experiment is that sample levels is placed on the electronic machine that shakes, and cloth twists in 100g/cm
2Move friction at sample surfaces under the pressure, check with universal meter whether coating weares and teares abrasion resistance=2 * vibrational frequency * time.
The experiment of scratch resistance trace is with iron nail or firmly delineation of pin.
Claims (4)
1, a kind of nitrogen protection prepares the method for titanium silicide film coating glass, it is characterized in that the step of this method is as follows:
1) reactant is SiH
4And TiCl
4, in the reaction chamber when off-line prepares with N
2Or in the molten tin bath in online when preparation with N
2, H
2Mixed gas is diluent gas and protective atmosphere;
2) SiH
4, TiCl
4And N
2Mix at mixing chamber; Each road gas equates that at the pressure of mixing chamber ingress pressure remains between 111325～131325Pa;
3) TiCl
4Constant temperature is at 30～70 ℃; TiCl
4Pipeline heat insulation to 40～80 ℃ of process;
4) by producer gas generator, use N
2Carry TiCl
4
5) SiH
4, TiCl
4And N
2Obtain reactant gases in the mixing chamber mixing;
6) volumetric molar concentration of each material in the reactant gases:
a)SiH
4：1～25％；
b)TiCl
4：0.1～10％；
C) SiH
4/ TiCl
4Mol ratio: 1～10;
D) N
2Or N
2, H
2Mixed gas: 50%～99%;
7) depositing system pressure is between 101325～131325Pa;
8) the glass substrate temperature is between 650～750 ℃, and reactant gases is transported on the glass substrate and reacts, and generates TiSi
2Film, growth for Thin Film speed are 10～50 nm/sec, and depositing time is 1～15 second;
9) waste gas is handled the back discharging through absorbing.
2, a kind of nitrogen protection according to claim 1 prepares the method for titanium silicide film coating glass, it is characterized in that: add the ethene or the methane of 1～20% volumetric molar concentration in reactant gases, form TiSi
2Composite SiC or TiSi
2The film of composite Ti C, the wear resistance and the chemical resistance of film further improve.
3, a kind of nitrogen protection according to claim 1 prepares the method for titanium silicide film coating glass, it is characterized in that: add the ammonia of 1～30% volumetric molar concentration in reactant gases, form TiSi
2Composite S i
3N
4Or TiSi
2The film of composite Ti N, the wear resistance and the chemical resistance of film further improve.
4,, be to go up deposition thin film (1), or between common float-glass substrate (2) and film (1), deposit one deck silicon film (3) again at common float-glass substrate (2) with the titanium silicide film coating glass of the described method preparation of claim 1; It is characterized in that:
Described film (1) is titanium silicide, titanium silicide composite S i, titanium silicide composite SiC or titanium silicide composite S i
3N
4
Titanium silicide in the described film (1) is the face-centered orthorhombic crystal structure, and the square resistance of film (1) is 1～100 Ω/.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100498287A CN1294098C (en) | 2005-05-25 | 2005-05-25 | Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100498287A CN1294098C (en) | 2005-05-25 | 2005-05-25 | Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1699235A CN1699235A (en) | 2005-11-23 |
| CN1294098C true CN1294098C (en) | 2007-01-10 |
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ID=35475520
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100498287A Expired - Fee Related CN1294098C (en) | 2005-05-25 | 2005-05-25 | Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100356522C (en) * | 2005-12-31 | 2007-12-19 | 浙江大学 | Method for preparing titanium silicide nano line by chemical gas phase deposition method |
| CN1872662B (en) * | 2006-04-24 | 2010-05-12 | 浙江大学 | Nano line cluster of titanium silicide prepared by chemical vapor deposition under normal pressure, and preparation method |
| CN101224951B (en) * | 2008-02-19 | 2011-06-01 | 浙江大学 | Nano-silicon composite carbon coated glass and quick-response on-line preparation method thereof |
| CN101475318B (en) * | 2009-01-19 | 2012-12-19 | 浙江大学 | Corrosion resistant titanium silicide film coating glass and preparation thereof |
| CN107833939B (en) * | 2017-11-22 | 2021-09-03 | 绍兴文理学院 | Two-dimensional photonic crystal selective radiator and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167986A (en) * | 1988-04-15 | 1992-12-01 | Gordon Roy G | Titanium silicide-coated glass windows |
| CN1534749A (en) * | 2003-02-21 | 2004-10-06 | ����ʿ�뵼������˾ | Semiconductor device having epitaxial C49 titanium silicide (TiSi2)layer and its manufacturing method |
-
2005
- 2005-05-25 CN CNB2005100498287A patent/CN1294098C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167986A (en) * | 1988-04-15 | 1992-12-01 | Gordon Roy G | Titanium silicide-coated glass windows |
| CN1534749A (en) * | 2003-02-21 | 2004-10-06 | ����ʿ�뵼������˾ | Semiconductor device having epitaxial C49 titanium silicide (TiSi2)layer and its manufacturing method |
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|---|---|
| CN1699235A (en) | 2005-11-23 |
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