CN103046023B

CN103046023B - Treatment furnace structure

Info

Publication number: CN103046023B
Application number: CN201110309596.XA
Authority: CN
Inventors: 萧盈诗; 吉村俊秋
Original assignee: HEXIN ENERGY INDUSTRIAL Co Ltd
Current assignee: HEXIN ENERGY INDUSTRIAL Co Ltd
Priority date: 2011-10-13
Filing date: 2011-10-13
Publication date: 2015-08-26
Anticipated expiration: 2031-10-13
Also published as: CN103046023A

Abstract

The treatment furnace structure that a kind of supplied gas reaction uses, comprise: an external furnace body, an inner furnace body, a heating arrangements, a gas supply mechanism, and a controlling organization, controlling air input by controlling organization can effectively make, the first pressure (P in inner furnace body flows outside space ₁), to be greater than inside inner furnace body the second pressure (P in reaction compartment all the time ₂).Design can make reactant gases flow velocity to accelerate thus, speeds film speed of reaction, and promotes film quality uniformity coefficient, also can promote rate of temperature fall simultaneously, increases processing safety.

Description

Treatment furnace structure

Technical field

The invention relates to a kind for the treatment of furnace structure, relate to one especially and perform heat treated heat treatment furnace under hyperbaric environment, heat treatment furnace is made to have the double space design of gas flow space (chamber) and reaction compartment, control by the relative density in double space or pressure, when the reactant gases in heat treatment furnace reaction compartment can be made to react under hyperbaric environment, reactant gases mixing is more even, in order to having accelerated reaction, and film former film quality is better, and lifting operation security.

Background technology

With the evolution of compound film solar battery process technology, existing more and more many product needed use thin-film technique equipment, substrate is grown up thin film or film precursor (Precursor).But the method being mainly used to grow films precursor at present has several, comprise sputtering method (Spattering), altogether vapour deposition method (Co-evaporation) etc.Particularly in compound film solar photoelectric related industries, successfully reach large-scale mass production person, mostly use sputtering method (Spattering) technology to carry out grow films precursor and carry out combination reaction formation film again.

In addition, combination reaction is carried out again in order to be formed in the technology of film Metalorganic chemical vapor deposition at film precursor, to provide gas phase compounds to carry out combination reaction most production to film precursor in heat treatment furnace, this is because, the reactive element of film precursor necessity is supplied in gas phase compounds mode, there is the advantage accurately controlling the diffusion of precursor concentration inside, make to carry out the correlation technique of film combination reaction with heat treatment furnace and equipment development more flourishing.Lift a concrete instance to illustrate: when copper-indium-gallium-selenium compound layer (CIGS) solar cell will carry out selenization process, namely be that the battery structure of the alloy of cupric, gallium and indium or multilayer precursor (Precusors) stacks of thin films of monomer formed on soda-lime glass (Soda Lime Glass) substrate via sputtering method (Spattering) deposition technique is delivered in selenizing stove (i.e. a kind of heat treatment furnace), and by Selenium hydride (H ₂se) gas passes into in selenizing stove, when the temperature in selenizing stove be heated to reach more than 400 DEG C time, Selenium hydride (H ₂se) namely gas start to react with multilayer precursor film; But, in the selenization process of CIGS solar cell, also need, by after battery structure stacking for multilayer film heating, sound response to be played with hydrogen selenide gas, and then the CIGS thin film layer obtained.Such as: after the CuGa/CuIn/In structure of the copper gallium alloy/copper and indium alloy/indium three layers of interactive stacking that complete, the stacking rete of CuGa/Cu In/In precursor of uniform film thickness can be obtained.Subsequently stacking for the CuGa/CuIn/In precursor of these three layers of interactive stackings rete is taken out, and move into immediately in selenizing stove, the Selenium hydride (H then passed into ₂se) gas, and with 40 DEG C/min heat-up rate to the heating of CuGa/CuIn/In precursor stacking rete, when temperature arrives 400 DEG C, copper gallium-indium alloy layer and selenium element reaction also transform into copper-indium-gallium-selenium compound layer.Then again with the heat-up rate Heated Copper gallium-indium alloy layer to 550 DEG C of 15 DEG C/min, to reach the best crystallization structure of copper-indium-gallium-selenium compound.Then, after the temperature in selenizing stove being reduced, the making of copper-indium-gallium-selenium compound layer can be completed.

Because selenization process can be heated in the ordinary course of things to 520 ~ 590 DEG C, but because known heat treatment furnace all uses huge thick silica tube as inner furnace body, and outer side edges directly with lagging material phase close contact, therefore in heat treatment furnace inside in closing state, again due under effects of expanding with heat and contract with cold, make furnace interior higher temperatures reactant gases up, comparatively low-temp reaction gas down, cause selenylation reaction uniformity coefficient not good, make copper-indium-gallium-selenium compound layer glass substrate film thickness everywhere and film quality different.Moreover the gas used due to selenization process (such as: Selenium hydride H ₂se gas), be poisonous, based on safe design, the pressure in its selenizing stove, in whole selenidation process, reacts, to avoid Selenium hydride H under being all only low pressure (namely must be less than 1atm) ₂se gas leaks outside, and causes work to pacify problem.But, when carrying out selenylation reaction under low pressure environment, easily cause gas molecule total quantity deficiency that the thermograde difference in selenizing stove is worsened, also the situation pockety of the molecular conecentration in selenizing stove is made more to worsen again, the situation of this kind of vicious cycle and then cause speed of reaction to be deteriorated simultaneously also to make film forming uniformity coefficient be deteriorated.Clearly, current selenizing stove, under the environment of low pressure and temperature inequality, generally can cause the concentration distribution of selenium uneven, also cause film former poor effect, and cause the photoelectric conversion rate of CIGS solar cell effectively to promote.

Then, please refer to Fig. 1 a and Fig. 1 b, is the known technology schematic diagram of the embodiment of U.S. Publication patent No. US7871502 patent of invention.Shown in Fig. 1 a, selenizing stove only has an airtight reaction compartment, and in order to provide the selenylation reaction of copper-indium-gallium-selenium compound layer, and in selenylation reaction process, the pressure in its reaction compartment is be less than a barometric point all the time; Again as shown in Figure 1 b, be the heating curve in selenylation reaction process.And carry out the temperature of selenylation reaction and pressure distribution schematic diagram as illustrated in figure 1 c in the selenizing stove shown in Fig. 1 a.After selenizing stove cuts out, need through extraction inner air repeatedly and send nitrogen to reaction compartment, to guarantee that reaction compartment in selenizing stove is entirely for nitrogen; Because traditional selenizing furnace foundation is in security consideration, mostly the pressure-controlling in reaction compartment is operated under low pressure (being namely less than 1atm), therefore in whole reaction process, the pressure in its reaction compartment is maintained between 0.8 ~ 0.9atm all the time.When raised temperature to 590 DEG C, because the gaseous tension in reaction compartment becomes large, therefore the object losing heart to reach pressure release for several times must be carried out, make internal pressure maintain target value; But, in these bleeding process, energy and excess gas can be wasted; When arriving temperature of reaction, namely send into reactant gases in reaction compartment; Generally 10%H can be used ₂se+90%N ₂(carrier gas) reacts.Can find out by Fig. 1 c, the selenylation reaction time is less than 100min and can completes reaction.Clearly, within the so short reaction times, the air-flow in reaction compartment cannot convection current and temperature distributing disproportionation, and selenylation reaction uniformity coefficient can be caused not good, make copper-indium-gallium-selenium compound layer substrate film thickness everywhere and film quality different.

After the combination reaction completing copper-indium-gallium-selenium compound layer, also need could take out CIGS solar cell substrate by after the temperature reduction in selenizing stove, but because in inner furnace body, reaction compartment is entirely enclosed space, only can slowly be filled with body of heater with nitrogen and air suction mode cooling simultaneously, therefore when the temperature in selenizing stove will be reduced to normal temperature, often take very of a specified duration; As illustrated in figure 1 c, generally about need 5 ~ 8hr, as substrate size amplify time, even take more than 10 hours, serious labor intensive and the material resources bottleneck simultaneously also in formation process.In addition, as shown in Figure 1a, gas piping and the Signal transmissions circuit design of selenizing stove are all positioned on gate, and during owing to carrying out technological operation at every turn, gate must be opened, and make pipeline easily get loose or break, and increase work safety dangerous.Namely the present invention attempts to improve for above-mentioned variety of problems, and proposes a new-type thermal reaction furnace design further.

Summary of the invention

The object of the present invention is to provide a kind for the treatment of furnace structure, to solve the problems referred to above existed in known technology.

For achieving the above object, the treatment furnace structure that supplied gas reaction provided by the invention uses, comprising:

One external furnace body, there is the second side of a first side and this first side relatively, and installing one can open the first gate on this first side, on this second side, install one can open the second gate, and the inner side of this first gate configuration one first airtight construction, and the inner side of this second gate configuration one second airtight construction;

One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of this external furnace body, make to form a gas flow space between this outer side wall of this inner furnace body and this external furnace body, and a reaction compartment is formed in this inner furnace body inner side-wall, this inner furnace body has the four side of one the 3rd side and the 3rd side relatively, when this first gate closes, this first airtight construction engages airtightly with the 3rd side, and the second airtight construction engages airtightly with this four side, make this gas flow space and each self-forming of this reaction compartment independently airtight space,

One heating arrangements, is fixedly arranged on this inner furnace body outer side wall, and contacts with this inner furnace body outer side wall; And a gas supply mechanism, be configured at the outside of this external furnace body, be connected with this external furnace body one side and this inner furnace body one side through multiple gas piping, controllably provide one first gas to this gas flow space with provide one second gas in this reaction compartment; And

One controlling organization, is configured at the outside of this external furnace body, provides this first gas and this second gas to the amount in this gas flow space and this reaction compartment in order to control this gas supply mechanism, makes this gas form one first pressure (P in the fluid-space ₁), and reaction compartment forms one second pressure (P ₂).

Described treatment furnace structure, wherein, the material of this external furnace body is for select by following composition: steel (steel), stainless steel (SUS304, SUS316).

Described treatment furnace structure, wherein, the material of this inner furnace body is for select by following composition: quartz, silicon-dioxide (SiO ₂).

Described treatment furnace structure, wherein, on a side of this first airtight construction and the 3rd side air tight contact, and this second airtight construction with on a side of this four side air tight contact, each self-forming one silicon-dioxide (SiO ₂) layer maybe can prevent corrode coating.

Described treatment furnace structure, wherein, is configured with at least one first sensor in this gas flow space, and each this first sensor is connected with this controlling organization.

Described treatment furnace structure, wherein, is configured with at least one second sensor in this reaction compartment, and each this second sensor is connected with this controlling organization.

Described treatment furnace structure, wherein, this first sensor and this second sensor are pressure warning unit.

Described treatment furnace structure, wherein, this first sensor and this second sensor are densometer.

Described treatment furnace structure, wherein, this heating arrangements is for select by following combination: graphite heater (carbon heater), halogen lamp.

Described treatment furnace structure, wherein, this first pressure (P ₁) be greater than a barometric point.

The treatment furnace structure that supplied gas reaction provided by the invention uses, also comprises:

One external furnace body, has the second side of a first side and this first side relatively, and on this first side, installs one can open the first gate, installs one and can open the second gate on this second side;

One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of this external furnace body, make to form a gas flow space between this outer side wall of this inner furnace body and this external furnace body, and a reaction compartment is formed in this inner furnace body inner side-wall, when this first gate and this second gate close, make this gas flow space and each self-forming of this reaction compartment independently airtight space;

One heating arrangements, is fixedly arranged on this inner furnace body outer side wall, and contacts with this inner furnace body outer side wall;

One gas supply mechanism, is configured at the outside of this external furnace body, is connected with this external furnace body one side and this inner furnace body one side through multiple gas piping, controllably provides one first gas to this gas flow space and provides one second gas in this reaction compartment; And

One controlling organization, provides this first gas and this second gas to the amount in this gas flow space and this reaction compartment in order to control this gas supply mechanism, makes this gas form one first pressure (P in the fluid-space ₁), and reaction compartment forms one second pressure (P ₂).

One external furnace body, there is the second side of a first side and this first side relatively, and the upper side to be connected with this first side and this second side and a downside, to form an accommodation space, and this first side configures openable first gate, and this second side is a sealing surface, inner side configuration one first airtight construction of this first gate;

One inner furnace body, compartment of terrain is fixedly arranged in the accommodation space of this external furnace body, there is an outer side wall and an inner side-wall, and there is the four side of one the 3rd side and the 3rd side relatively, and this four side is connected with this sealing surface, make to form a gas flow space between this outer side wall of this inner furnace body and this external furnace body, and a reaction compartment is formed in this inner furnace body inner side-wall, when this first gate closes, this first airtight construction engages airtightly with the 3rd side, makes this gas flow space and each self-forming of this reaction compartment independently airtight space;

One gas supply mechanism, be configured at the outside of this external furnace body, be connected with this downside of this external furnace body and this outer side wall of this inner furnace body through multiple gas piping, controllably provide one first gas to this gas flow space and provide one second gas in this reaction compartment; And

Described treatment furnace structure, wherein, on a side of this first airtight construction and the 3rd side air tight contact, forms a silicon-dioxide (SiO ₂) layer.

Described treatment furnace structure, wherein, carries out in gas reaction process in this treatment furnace structure, controls this gas flow space first pressure (P by this controlling organization ₁) be greater than the second pressure (P of this reaction compartment all the time ₂).

The multistage heat treatment furnace that supplied gas reaction provided by the invention uses, be connected in series by multiple heat treatment furnace and formed, wherein, each treatment furnace structure comprises:

One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of this external furnace body, make to form a gas flow space between this outer side wall of this inner furnace body and this external furnace body, and a reaction compartment is formed in this inner furnace body inner side-wall, this inner furnace body has the four side of one the 3rd side and the 3rd side relatively, when this first gate closes, this first airtight construction engages airtightly with the 3rd side, and the second airtight construction engages airtightly with this four side, make this gas flow space and this reaction compartment self-forming independently airtight space,

Described treatment furnace structure, wherein, this gas flow space is configured with at least one first sensor, and each this first sensor is connected with this controlling organization.

Via treatment furnace structure provided by the present invention; owing to increasing the design of a gas flow space between inner furnace body and external furnace body; can available protecting operator safety; speed reaction rate of film build and film quality homogeneity; and more effectively accelerate rate of temperature fall; use manpower and material resources sparingly, and the reaction environment of high pressure gas is provided, be beneficial to user and use in time generating various film.

Accompanying drawing explanation

Fig. 1 a is known technology schematic diagram;

Fig. 1 b is known technology schematic diagram;

Fig. 1 c is temperature and the pressure distribution schematic diagram of known technology;

Fig. 2 is the schematic diagram of an embodiment for the treatment of furnace structure of the present invention;

Fig. 3 is the diagrammatic cross-section of an embodiment for the treatment of furnace structure of the present invention;

Fig. 4 is the schematic top plan view of the gate opening mode of an embodiment for the treatment of furnace structure of the present invention;

Fig. 5 is the schematic diagram of another embodiment for the treatment of furnace structure of the present invention;

Fig. 6 is that the pressure for the treatment of furnace structure of the present invention and temperature control distribution schematic diagram;

Fig. 7 is that the density for the treatment of furnace structure of the present invention and temperature control distribution schematic diagram.

Fig. 8 is the embodiment schematic diagram of multistage treatment furnace structure of the present invention.

Primary clustering nomenclature in accompanying drawing:

Treatment furnace structure 1; Treatment furnace structure 2; Thin-film solar cell substrate 3;

External furnace body 10; First side 101; Second side 102;

First gate 1001; First airtight construction 10011; Locking part 10012; Deoscillator 10013; Gas seal member 10014;

Second gate 1002; Second airtight construction 10021;

First sensor 103;

Inner furnace body 20; 3rd side 201; Four side 202; Second sensor 203; The fluid-space 204; Reaction compartment 205;

Heating arrangements 30;

Gas supply mechanism 40;

Controlling organization 50;

Through hole 60;

Safety valve 70;

Obturator 80.

Embodiment

In treatment furnace structure of the present invention, in between inner furnace body and external furnace body, increase by a gas flow space, make between external furnace body and inner furnace body, to maintain a pressure difference, and inner furnace body reactant gas molecules density or gaseous tension are improved, speed the film chemical combination reaction times, and promote film quality uniformity coefficient.

In treatment furnace structure of the present invention, in between inner furnace body and external furnace body, increase by a gas flow space, make cooling nitrogen enter reaction compartment in inner furnace body simultaneously, and gas flow space between inner furnace body and external furnace body, and can nitrogen flow rate be accelerated, effectively and speed rate of temperature fall.

In treatment furnace structure of the present invention; increase by a gas flow space between inner furnace body and external furnace body; make cooling nitrogen enter reaction compartment in inner furnace body simultaneously; and gas flow space between inner furnace body and external furnace body; make inner furnace body furnace wall to produce thermograde, available protecting inner furnace body limit wall is avoided be full of cracks or is peeled off.

In treatment furnace structure of the present invention; a gas flow space is had more between inner furnace body and external furnace body; and be filled with nitrogen and make gas flow space pressure (P1) slightly larger than reaction compartment gaseous tension (P2) in inner furnace body; and set up a safety valve; can available protecting operator safety; make heat treatment furnace not because of internal-response imbalance of pressure, and cause operator dangerous.

In treatment furnace structure of the present invention, a gas flow space is had more between inner furnace body and external furnace body, due to can effectively lifting operation security, can lifting operation pressure be not limited to low pressure (< 1atm) environment under operate, can operate under high pressure (> 1atm) environment further, more effectively can promote speed of reaction and film quality homogeneity, and avoid the waste of reactant gases.

Treatment furnace structure of the present invention, wherein comprises a sensor, makes in film former process, be able to reaction compartment pressure in Real-Time Monitoring inner furnace body, gas flow space pressure, effectively controls in order to do being beneficial to and adjusts air input, makes security promote and make film former effect better.

Treatment furnace structure of the present invention, owing to being both lateral sides perforate design, in a joint manner, can connect multiple heat treatment furnace, effectively saves equipment cost in the lump, and shipment and delivery cost, more can increase productivity effect, lifting gear reliability.

Treatment furnace structure of the present invention, its control mode can be selected in pressure measurement pressure measurement difference mode or in the gas density mode of densitometry measured reaction space and gas flow space, carry out subsequent control by after Signal transmissions to operating device, more can increase productivity effect, avoid wasting excessive gas.

The treatment furnace structure that supplied gas reaction provided by the invention uses, comprising: an external furnace body, have first side and second side, and installing one can open the first gate on first side, install one and can open the second gate on second side; One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of external furnace body, make between the outer side wall of inner furnace body and external furnace body, to form a gas flow space, and a reaction compartment is formed in inner furnace body inner side-wall, when the first gate and the second gate close, make gas flow space and each self-forming of reaction compartment independently airtight space; One heating arrangements, is fixedly arranged on inner furnace body outer side wall, and contacts with inner furnace body outer side wall; And a gas supply mechanism, be configured at the outside of external furnace body, be connected with external furnace body one side and inner furnace body one side through multiple gas piping, controllably provide one first gas in this gas flow space and one second this reaction compartment of gas; One controlling organization, provides the first gas and the second gas to the amount in gas flow space and reaction compartment in order to control gas supply mechanism, makes gas form the first pressure (P in the fluid-space ₁), and reaction compartment forms the second pressure (P ₂); Wherein carry out in gas reaction process in treatment furnace structure, controlled the first pressure (P of gas flow space by controlling organization ₁) be greater than the second pressure (P of reaction compartment 205 all the time ₂).

The present invention also provides a kind of supplied gas to react the treatment furnace structure used, comprise: the treatment furnace structure that a kind of supplied gas reaction uses, comprise: an external furnace body, there is the second side of a first side and relative first side, and installing one can open the first gate on first side, on second side, install one can open the second gate, and the inner side of the first gate configuration one first airtight construction, and the inner side of the second gate configuration one second airtight construction; One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of external furnace body, make between the outer side wall of inner furnace body and external furnace body, to form a gas flow space, and a reaction compartment is formed in inner furnace body inner side-wall, inner furnace body has the four side of one the 3rd side and relative 3rd side, when the first gate closes, first airtight construction engages airtightly with the 3rd side, and the second airtight construction engages airtightly with four side, make gas flow space and each self-forming of reaction compartment independently airtight space; One heating arrangements, is fixedly arranged on inner furnace body outer side wall, and is close to mutually with inner furnace body outer side wall; And a gas supply mechanism, be configured at the outside of external furnace body, be connected with external furnace body one side and inner furnace body one side through multiple gas piping, controllably provide one first gas to gas flow space and one second gas in reaction compartment; One controlling organization, is configured at the outside of external furnace body, provides the first gas and the second gas to the amount in gas flow space and reaction compartment in order to control gas supply mechanism, makes gas form one first pressure (P in the fluid-space ₁), and reaction compartment 205 forms one second pressure (P ₂).

The present invention also provides a kind of supplied gas to react the treatment furnace structure used, comprise: an external furnace body, there is the second side of a first side and relative first side, and the upper side to be connected with first side and second side and a downside, to form an accommodation space, and first side configures an openable gate, and second side is a sealing surface, inner side configuration one first airtight construction of the first gate; One inner furnace body, compartment of terrain is fixedly arranged in the accommodation space of external furnace body, there is an outer side wall and an inner side-wall, and there is the four side of one the 3rd side and relative 3rd side, and four side is connected with sealing surface, make between the outer side wall of inner furnace body and external furnace body, to form a gas flow space, and a reaction compartment is formed in inner furnace body inner side-wall, when the first gate closes, first airtight construction engages airtightly with the 3rd side, makes gas flow space and each self-forming of reaction compartment independently airtight space; One heating arrangements, is fixedly arranged on inner furnace body outer side wall, and contacts with inner furnace body outer side wall; And a gas supply mechanism, be configured at the outside of external furnace body, be connected with the downside of external furnace body and the outer side wall of inner furnace body through multiple gas piping, controllably provide one first gas to gas flow space and one second gas in reaction compartment; One controlling organization, is configured at the outside of external furnace body, provides the first gas and the second gas to the amount in gas flow space and reaction compartment in order to control gas supply mechanism, makes gas form one first pressure (P in the fluid-space ₁), and reaction compartment forms one second pressure (P ₂).

The present invention also provides a kind of supplied gas to react the multistage heat treatment furnace used, be connected in series by multiple heat treatment furnace and formed, wherein, each treatment furnace structure comprises: an external furnace body, there is first side and second side, and installing one can open the first gate on first side, on second side, install one can open the second gate, and the inner side of the first gate configuration one first airtight construction, and the inner side of the second gate configuration one second airtight construction; An inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of external furnace body, make to form a gas flow space between the outer side wall of inner furnace body and external furnace body, and a reaction compartment is formed in inner furnace body inner side-wall, and inner furnace body has one the 3rd side and four side, when the first gate closes, first airtight construction engages airtightly with the 3rd side, and the second airtight construction engages airtightly with four side, make gas flow space and each self-forming of reaction compartment independently airtight space; A heating arrangements, is fixedly arranged on inner furnace body outer side wall, and contacts with inner furnace body outer side wall; A gas supply mechanism, is configured at the outside of external furnace body, is connected with external furnace body one side and inner furnace body one side through multiple gas piping, controllably provides the first gas to gas flow space 4 and the second gas in reaction compartment; And a controlling organization, be configured at the outside of external furnace body, provide the first gas and the second gas to the amount in gas flow space and reaction compartment in order to control gas supply mechanism, make gas form one first pressure (P in the fluid-space ₁), and reaction compartment forms one second pressure (P ₂).

Because the present invention mainly provides a kind of structure about treatment furnace structure and function, for ease of illustrating, follow-up is be described with the treatment furnace structure of the thin-film solar cells of one making copper-indium-gallium-selenium compound layer (CIGS); Wherein, there are the structure about the treatment furnace structure of the thin-film solar cells making copper-indium-gallium-selenium compound layer and effect thereof, for those skilled in the art can understand, therefore with explanation hereinafter, be only described in detail for the feature place with treatment furnace structure of the present invention.Meanwhile, with hereinafter contrasted accompanying drawing, be express the structural representation relevant with feature of the present invention, therefore do not draw according to physical size, chat bright in advance.

First, please refer to Fig. 2, is the embodiment schematic diagram of a kind for the treatment of furnace structure of the present invention.As shown in Figure 2, heat treatment furnace comprises: an external furnace body 10, there is the second side 102 of first side 101 and relative first side 101, and openable first gate 1001 is installed in first side 101, openable second gate 1002 is installed in second side 102, and the inner side of the first gate 1001 configures first airtight construction 10011, and the inner side of the second gate 1002 can also option and installment second airtight construction 10021; In an embodiment of the present invention, the first airtight construction 10011 and the second airtight construction 10021 comprise a locking part 10012 and a deoscillator 10013 (damper) and a gas seal member 10014, and wherein gas seal member 10014 material can be rubber; An inner furnace body 20, there is the four side 202 of the 3rd side 201 and relative 3rd side 201, and there is an outer side wall 21 and an inner side-wall 22, compartment of terrain is fixedly arranged between the inner side-wall 12 of external furnace body 10, make between the outer side wall 21 of inner furnace body 20 and the inner side-wall 12 of external furnace body 10, to form a gas flow space 204, and form a reaction compartment 205 in inner furnace body 20 inner side-wall 22; A heating arrangements 30, is fixedly arranged on inner furnace body 20 outer side wall 21, and contacts with inner furnace body 20 outer side wall 21; And a gas supply mechanism 40, be configured at the outside of external furnace body 10, be connected with a side of external furnace body 10 and a side of inner furnace body 20 through multiple gas piping, therefore gas can be provided in gas flow space 204 and reaction compartment 205; A controlling organization 50, be configured at the outside of external furnace body 10 and be connected with the pipeline in gas supply mechanism 40, in order to provide gas to deliver to gas flow space 204 and the amount in reaction compartment 205, and accurately can control gas and form the first pressure (P in the fluid-space 204 ₁), and form the second pressure (P in reaction compartment 205 ₂); Or make gas have the first density in the fluid-space 204, and there is in reaction compartment 205 performance characteristic of the second density.

When the first gate 1001 and the second gate 1002 are closed, by the first airtight construction 10011 and the second airtight construction 10021, the first side 101 of heat treatment furnace and second side 102 are closed; Simultaneously, first airtight construction 10011 is via three side 201 airtight joint of gas seal member 10014 with inner furnace body 20, and the second airtight construction 10021 is also via four side 202 airtight joint of gas seal member 10014 with inner furnace body 20, make the gas flow space 204 between external furnace body 10 inner side-wall 12 and inner furnace body 20 outer side wall 21, and two separate space that each self-forming of reaction compartment 205 between inner furnace body 20 inner side-wall 22 does not communicate.

Heat treatment furnace of the present invention, in the process forming copper-indium-gallium-selenium compound layer, must pass into Selenium hydride (H ₂se) gas is in the reaction compartment 205 of inner furnace body 20, and uses high temperature and high-pressure process could form the copper-indium-gallium-selenium compound layer of high evenness; In addition, Selenium hydride (H to reaction compartment 205 is passed into ₂se) gas can generate tin anhydride (SeO with air vigorous reaction ₂) dust, this tin anhydride dust can pollute the furnace wall of copper-indium-gallium-selenium compound layer quality and inner furnace body 20 inner side-wall 22, and be easy to cause personnel hazard's property, therefore in reaction process, gas flow space 204 between external furnace body 10 and inner furnace body 20 and the reaction compartment 205 between inner furnace body 20 inner side-wall 22 need maintain sealing gland state, simultaneously two separate space that do not communicate of each self-forming.Therefore, the material of the external furnace body 10 of heat treatment furnace of the present invention is for select by following composition: steel (steel) or stainless steel (such as: SUS304, SUS316), makes external furnace body 10 of the present invention resistance toly can be depressed into 20atm; But, do not limit external furnace body 10 in the present invention and form material; In addition, the present invention can also configure heat insulation material further on the inner side-wall 12 of external furnace body 10, makes to carry out in heat-processed, if can not be passed to the outer side wall 11 of external furnace body 10; And this heat insulation material can be the high temperature resistant material such as quartz brick or mica brick.

Then, please refer to Fig. 3, is the diagrammatic cross-section for the treatment of furnace structure of the present invention.As shown in Figure 3, the heating arrangements 30 of heat treatment furnace of the present invention is listed on inner furnace body 20 outer side wall 21 by multiple well heater (heater), and be close to mutually with inner furnace body 20 outer side wall 21, wherein, heating arrangements 30 is for select by following combination: graphite heater (carbon heater) or halogen lamp, temperature of reaction is made to be increased to set(ting)value for heating internal protecting wall, wherein graphite heater can be with hot water radiation wire type of heating, and halogen lamp is infrared heating mode, all inner furnace body 20 is had to the function of evenly heating.In a preferred embodiment, when reactant gases is Selenium hydride H ₂during Se, can heat to 520 ~ 590 DEG C and react.Referring again to Fig. 3, by the accurate location can finding out reaction compartment 205 and gas flow space 204 and internal-response substrate in figure, substrate is that longitudinal arrangement mode enters, coordinate internal gas flow flow direction, make film formation reaction result more even, in figure, reserved two through hole 60 uses as gas piping passage and signal transmission line paths.In addition, due to inner furnace body 20 need under High Temperature High Pressure environmental operations, and reactant gases is (such as: Selenium hydride H ₂se) possibility tool corrodibility; So the material of the inner side-wall 22 of inner furnace body 20 can be: quartz or silicon-dioxide (SiO ₂), can not be corroded to protect inner furnace body 20 further.

Again then, please refer to Fig. 4, is the schematic top plan view of the gate opening mode of heat treatment furnace of the present invention.As shown in Figure 4, when the first gate 1001 closes, the 3rd side 201 airtight joint of the first airtight construction 10011 and inner furnace body 20, and when the second gate 1002 closes, four side 202 airtight joint of the second airtight construction 10021 and inner furnace body 20; Meanwhile, when the first gate 1001 and the second gate 1002 close, deoscillator 10013 and gas seal member 10014 can, by the elasticity of deoscillator 10013, make gas seal member 10014 to produce airtight conditions; After the first gate 1001 and the second gate 1002 close, when locking part 10012 can be used to lock integral by the first side 101 of the first gate 1001 and the second gate 1002 and external furnace body 10 and second side 102, the gas flow space 204 between external furnace body 10 and inner furnace body 20 and the reaction compartment 205 between inner furnace body 20 inner side-wall 22 can be made to maintain airtight conditions.In addition, on the side that the first airtight construction 10011 contacts with the 3rd side 201, and on the side contacted with four side 202 of the second airtight construction 10021, a silicon-dioxide (SiO can be all coated with ₂) layer maybe can prevent corrode coating, as protection gate in case by reactant gases corrosion use.

Again as shown in Figure 4, heat treatment furnace of the present invention its when general operation uses, only can open a gate (such as: the first gate 1001), opposite side gate (such as: the second gate 2001) then maintain locking and close dress state.And open opposite side gate just now when treatment furnace structure 1 needs repairing.

Again emphasize, when airtight conditions is formed, gas flow space 204 of the present invention and reaction compartment 205, be each self-forming independently airtight space, two space gases can not circulate mutually.Clearly, treatment furnace structure of the present invention and known technology one of do not exist together, be that heat treatment furnace of the present invention need not configure gas piping passage and signal transmission line paths on the first gate 1001, therefore heat treatment furnace of the present invention is in charging and discharging process, the unlatching of the first gate 1001 or closedown, all can not on the structural strength affecting gas supply mechanism 40, therefore except increasing except the reliability for the treatment of furnace structure, the gas piping that can also reduce gas supply mechanism 40 produces the work peace doubt of gas leakage, can be easier when can make thermal reaction furnace structure fabrication simultaneously.

Refer again to Fig. 2, in gas flow space 204, be configured with at least one first sensor 103, and each first sensor 103 is connected with controlling organization 50; Meanwhile, in reaction compartment 205, be configured with at least one second sensor 203 equally, and each second sensor 203 is also connected with controlling organization 50.When first sensor 103 and the second sensor 203, when being all pressure warning unit, can respectively by gas flow space 204 the pressure (P1) that measures and reaction compartment 205 the pressure (P2) that measures deliver in controlling organization 50, then calculate pressure difference (P by controlling organization 50 ₁-P ₂), and control further.It is special it is emphasized that the present invention calculates pressure difference (P by controlling organization 50 ₁-P ₂) object, be via first sensor 103 and the second sensor 203 pairs of gas flow space 204 and reaction compartment 205 pressure difference (P between the two ₁-P ₂) do and accurately control, particularly control the pressure of pressure slightly larger than internal-response space 205 of outer flow space 204.Such as: in one embodiment of this invention, its original start pressure difference value is set as 1Kg/cm ², namely as (P ₁-P ₂) pressure difference be greater than 1Kg/cm ²time, namely controlling organization 50 can adjust and increase reaction compartment 205 air input, also can adjust and reduce the fluid-space 204 air input simultaneously, gas flow space 204 and reaction compartment 205 pressure difference between the two (P1-P2) are remained between the scope of a setting.And in a preferred embodiment, the pressure of outer flow space 204 is greater than a normal atmosphere (1atm).Clearly, based on security consideration, in the present embodiment, the control of pressure reduction is that the while of adopting two spaces (i.e. gas flow space and reaction compartment), intake method carries out.

Again as shown in Figure 2, the present invention configures a safety valve 70 between the two further in gas flow space 204 and reaction compartment 205, such as: safety valve 70 to be configured between inner furnace body 20 outer side wall 21 and inner side-wall 22 (thickness wherein, between the outer side wall 21 of inner furnace body 20 and inner side-wall 22 is between 6 ~ 25mm); As reaction compartment 205 pressure (P ₂) be greater than gas flow space 204 pressure (P ₁) set(ting)value time, now safety valve 70 can be broken, and gas flow space 204 and reaction compartment 205 gas are circulated; And because the pressure of the fluid-space 204 is slightly larger than the cause of the pressure of reaction compartment 205, hydrogen selenide gas in the fluid-space 204 can be extruded in reaction compartment 205, therefore can not leak to the external world, and the design of safety valve 70 also makes treatment furnace structure 1 not have excess pressure generation, and the phenomenon destroying the quartzy furnace wall of inner furnace body 20 occurs.In an embodiment of the present invention, General reactions space 205 operating pressure can operate in 5atm, and this operating pressure is far below outer boiler tube institute withstand voltage 20atm, and therefore heat treatment furnace of the present invention can guarantee processing safety.

The safety Design of heat treatment furnace of the present invention is now illustrated for an embodiment.Be 3atm when first sensor 103 measures the fluid-space 204 pressure, second sensor 203 measures reaction compartment 205 pressure is simultaneously 2atm, and external atmospheric pressure is when being 1atm, that is the fluid-space 204 pressure is greater than reaction compartment 205 pressure and external atmospheric pressure simultaneously, therefore when there is gas leakage, according to the design of heat treatment furnace of the present invention, due to pressure reduction cause, gas (such as: nitrogen) in the fluid-space 204 can be leaked to the external world by it, now reaction compartment 205 pressure also can because of the decline of pressure in the fluid-space 204, controlling organization can maintain its pressure reduction in the future by under reaction compartment 205 pressure, therefore the upper doubt of safety can't be produced to operator.Because security promotes cause, treatment furnace structure 1 of the present invention all can be able to operate in low pressure environment and normal pressure, hyperbaric environment, and its suitable operation pressure interval is 0.5 ~ 9.8atm.

But, in the structure of heat treatment furnace of the present invention, if for the fluid-space 204 is operating under 1atm with the pressure in reaction compartment 205 time; Such as: the fluid-space 204 pressure is 1atm, and reaction compartment 205 pressure is 0.98atm; Heat treatment furnace of the present invention to perform in this operating condition.

In addition, if when first sensor 103 and the second sensor 203, measurement gas density mode can be adopted when being all densometer to be controlled reaction, and control mode adopts ripple with ear equation principle: P _av _a/ T _a=P _bv _b/ T _b(wherein P _a, V _a, and T _abe respectively pressure, the volume under a point, and temperature; P _b, V _b, and T _bbe respectively pressure, the volume under b point, and temperature), having can statement in detail in aftermentioned Fig. 6 and Fig. 7 about detailed control mode.If first sensor 103 and the second sensor 203, for density take into account pressure warning unit composition time, user can select to adopt pressure-controlling or density domination mode, controls reaction, this place is not limited actual employing control status, and should be as the criterion with actually operating case.

According to aforementioned, gas supply mechanism 40 of the present invention, is configured at the outside of external furnace body 10, is connected with a side of external furnace body 10 and a side of inner furnace body 20 through multiple gas piping, can control and provide at least one first gas (such as: nitrogen N ₂, argon Ar) to gas flow space 204; And control and provide at least one second gas (such as: hydrogen H ₂, nitrogen N ₂, Selenium hydride H ₂se, hydrogen sulfide H ₂s, argon Ar) in reaction compartment 205, to carry out subsequent reactions.In addition, controlling organization 50 of the present invention, be be configured at external furnace body 10 outside and be connected with the pipeline in gas supply mechanism 40, there is provided the first gas and the second gas to gas flow space 204 and the amount in reaction compartment 205 in order to control gas supply mechanism 40, make gas form the first pressure (P in the fluid-space 204 ₁), and reaction compartment 205 forms the second pressure (P ₂).Be noted that the present invention carries out in gas reaction process in treatment furnace structure 1 especially, controlled the first pressure (P in gas flow space 204 by controlling organization 50 ₁) be the second pressure (P be greater than all the time in reaction compartment 205 ₂); Or the first density controlling gas flow space 204 is greater than the second density of reaction compartment 205 all the time.And in one embodiment, the first pressure (P ₁) can by the interval of control 0.5 ~ 9.8atm.In addition, controlling organization 50 of the present invention is except controlling air input, also can detect and further control pressure, temperature, density, toxicity, time, gaseous species etc. simultaneously, that is all controls relevant with heat treatment furnace are all via pressure transmitter, density sensor, temperature sensor (not shown), toxic sensors (not shown), transfer to controlling organization 50 be further processed after measurement by signal transmission line.

Please refer to Fig. 5, is another embodiment schematic diagram for the treatment of furnace structure 2 of the present invention.As shown in Figure 5, treatment furnace structure 2 comprises: an external furnace body 10, there is an outer wall 11 and an inwall 12, and there is the second side 102 of first side 101 and relative first side 101, and the upper side to be connected with first side 101 and second side 102 and downside, to form an accommodation space, and first side 101 configures an openable gate 1001, and second side 102 is a sealing surface, the inner side of gate 1001 configures an airtight construction 10011; An inner furnace body 20, compartment of terrain is fixedly arranged in the accommodation space of external furnace body 10, there is an outer side wall 21 and an inner side-wall 22, and there is the four side 202 of the 3rd side 201 and relative 3rd side 201, and four side 202 is connected with sealing surface, make to form a gas flow space 204 between the outer side wall 21 of inner furnace body 20 and the inwall 12 of external furnace body 10, and form a reaction compartment 205 in inner furnace body 20 inner side-wall 22; Therefore when gate 1001 closes, its airtight construction 10011 engages airtightly with the 3rd side 201, make gas flow space 204 and each self-forming of reaction compartment 205 independently airtight space; A heating arrangements 30, is fixedly arranged on inner furnace body 20 outer side wall 21, and contacts with inner furnace body 20 outer side wall 21; A gas supply mechanism 40, is configured at the outside of external furnace body 10, is connected with the downside of external furnace body 10 and the outer side wall of inner furnace body 20 through multiple gas piping, can provide at least one first gas (such as: nitrogen N ₂, argon Ar) to gas flow space 204, and can provide at least one second gas (such as: hydrogen H ₂, nitrogen N ₂, Selenium hydride H ₂se, hydrogen sulfide H ₂s, argon Ar) in reaction compartment 205; And a controlling organization 50, be configured at the outside of external furnace body 10 and be connected with the pipeline in gas supply mechanism 40, there is provided the first gas and the second gas to gas flow space 204 and the amount in reaction compartment 205 in order to control gas supply mechanism 40, make gas form the first pressure (P in the fluid-space 204 ₁), and reaction compartment 205 forms the second pressure (P ₂).

Clearly, the treatment furnace structure 2 shown in Fig. 5 its only have an openable gate 1001 be not identical with the embodiment (i.e. treatment furnace structure 1) shown in earlier figures 2 outside, remaining structure is all identical with the treatment furnace structure 1 shown in Fig. 2; Wherein, the material of external furnace body 10 is for select by following composition: steel (steel), stainless steel (SUS304, SUS316); And inner furnace body 20 is due to need under high temperature and high pressure environment, and reactant gases may tool corrodibility, therefore use material for select by following composition: quartzy, silicon-dioxide (SiO ₂), and on a side of wherein the first airtight construction 10011 and the 3rd side 201 air tight contact, form a silicon-dioxide (SiO equally ₂) layer, for protection first gate 1001.In addition, in the gas flow space 204 of the present embodiment, be configured with at least one first sensor 103, and each first sensor 103 is connected with controlling organization 50, and in reaction compartment 205, be configured with at least one second sensor 203, and each second sensor 203 is connected with controlling organization 50; Similarly, if when the present embodiment adopts under pressure-controlling, then first sensor 103 and the second sensor 203 a kind of pressure warning unit; And when if the present embodiment adopts density domination, then first sensor 103 and the second sensor 203 a kind of densometer; In addition, the present embodiment also can select first sensor 103 for pressure warning unit and and the second sensor 203 treatment furnace structure 2 is controlled for densometer, therefore user can be provided to look actually operating gas station switch and use.Similarly, in the present embodiment, carry out in gas reaction process in treatment furnace structure 2, can select by controlling organization 50 to control the first pressure (P of gas flow space 204 ₁) be greater than the second pressure (P of reaction compartment 205 all the time ₂); Or the first density controlling gas flow space 204 is greater than the second density of reaction compartment 205 all the time.Because embodiment (the i.e. treatment furnace structure 1) distributing style between external furnace body 10 and inner furnace body 20 shown in the present embodiment with Fig. 2 is identical, therefore the various safe design of the aforesaid embodiment to treatment furnace structure 1, all be applicable to the present embodiment, therefore do not repeat them here.

Clearly, treatment furnace structure of the present invention and known technology one of do not exist together, be that heat treatment furnace of the present invention need not configure gas piping passage and signal transmission line paths on gate 1001, therefore heat treatment furnace of the present invention is in charging and discharging process, the unlatching of gate 1001 or closedown, all can not on the structural strength affecting gas supply mechanism 40, therefore except increasing except the reliability for the treatment of furnace structure, the gas piping that can also reduce gas supply mechanism 40 produces the work peace doubt of gas leakage, can be easier when can make thermal reaction furnace structure fabrication simultaneously.

Then, please refer to Fig. 6, is temperature and the pressure distribution schematic diagram of thermal reaction furnace of the present invention.As shown in Figure 6, after gate 1001 and gate 1002 are closed, meeting control gas supply mechanism 40 pairs of gas flow space 204 by controlling organization 50 and reaction compartment 205 carries out bleeding and (such as: pass into nitrogen) process of ventilating, to confirm exist without aqueous vapor in body of heater reaction compartment 205 of several; Simultaneously, treatment furnace structure 1 starts slow intensification degree and adds reactant gases; In the present embodiment, the gas be added in reaction compartment 205 is: 10%H ₂se+90%N ₂(carrier gas).As seen from Figure 6, in temperature-rise period, after the time proceeds to 50min, namely arrive a weight break point (such as: be heated to 300 DEG C), namely no longer add reactant gases, and only raised temperature.This is with ear equation principle: P according to ripple _av _a/ T _a=P _bv _b/ T _b(wherein P _a, V _a, and T _abe respectively pressure, the volume under a point, and temperature; P _b, V _b, and T _bbe respectively pressure, the volume under b point, and temperature), can before starting to operate heat treatment furnace, namely the amount of reactant gases that need be provided in reaction compartment 205 has been calculated, therefore add to the amount calculated in reactant gases after, namely no longer continue to add reactant gases, and only continue raised temperature.

Along with the quick rising of temperature, the pressure in reaction compartment 205 will be made also to raise rapidly, such as: after temperature is increased to temperature of reaction 590 DEG C, the pressure in reaction compartment 205 also can arrive near 5atm; Then, namely reactant gases can react under temperature is 590 DEG C and pressure is 5atm; Clearly, now controlling organization 50 can by the pressure-controlling in gas flow space 204 at 5.1atm; As shown in Figure 6, the reaction times of the present embodiment is about 20min and can completes; Again then, carry out fast cooling technique immediately, now, the nitrogen of cooling is delivered in gas flow space 204 and reaction compartment 205 is simultaneously lowered the temperature after gas unreacted in reaction compartment 205 being detached by controlling organization 50 immediately again; Because embodiments of the invention are lowered the temperature in both sides, inner furnace body 20 furnace wall simultaneously, make under identical nitrogen flow, rate of temperature fall is at least original rate of temperature fall twice, and the doubt owing to chapping without inner furnace body 20 furnace wall or peeling off, more can accelerate feed rate and air input, effective lifting rate of temperature fall, shortens temperature fall time; Again as shown in Figure 6, thermal reaction furnace 1 of the present invention only needs 120 minutes, temperature in reaction compartment 205 can be down to design temperature from 590 DEG C is 50 ~ 60 DEG C, therefore gate 1001 can be opened, the thin-film solar cell substrate 3 of the copper-indium-gallium-selenium compound layer (CIGS) completing selenylation reaction is taken out.

Process described above, because the present invention can adopt pressure measurement mode, reaction is controlled, after measuring reaction compartment 205 in advance via first sensor 103 and the second sensor 203 and measuring the pressure in gas flow space 204, again measuring value is reached controlling organization 50 by signal transmission line, carried out controlling (namely controlling the force value of the force value in gas flow space 204 slightly larger than reaction compartment 205) according to the pressure difference value in reaction compartment 205 and gas flow space 204 by controlling organization 50, the reaction in reaction compartment 205 is carried out smoothly.Therefore thermal reaction furnace 1 of the present invention is in the process be rapidly heated, do not need to carry out pressure release action, and selenylation reaction can be carried out under high pressure due to thermal reaction furnace structure of the present invention; Example: 5atm; Therefore can effectively accelerated reaction carry out, the reaction times is shortened; Such as, in the present embodiment, the reaction times is about 20min; In addition, another advantage of the present invention is temperature-fall period, and about only needing 120min to be namely down to design temperature is 50 ~ 60 DEG C.Clearly, according to Fig. 6, thermal reaction furnace 1 of the present invention, except shortening except the time of selenylation reaction, can also shorten the time of cooling significantly, therefore can accelerate the rate of utilization of thermal reaction furnace 1, and then obviously reduces the cost manufactured.

Then, please refer to Fig. 7, is the temperature-density distribution schematic diagram of the density domination of thermal reaction furnace of the present invention.As shown in Figure 7, in the present embodiment, operational condition is: when inner furnace body 20 diameter is 1.1m, and long is 2m, and when in the reaction compartment 205 of inner furnace body 20, shared by real gas, volume is about 1235lithers; When after the upper lock gate 1001 of pass, because the longitudinal axis is density, therefore when shutting valve 1001 and after being filled with nitrogen, initial stage is greater than the factor of density of nitrogen because of the density of air, therefore the density of nitrogen is lower, after bleeding for several times and being filled with nitrogen procedure, confirm that inside is without after aqueous vapor, passes into reactant gases 10%H immediately ₂se+90%N ₂(carrier gas), start to heat up simultaneously, identical with earlier figures 7 heat treatment furnace pressure-controlling temperature, pressure distribution schematic diagram, after the time proceeds to 50min (such as: be heated to 300 DEG C), namely no longer pass into reactant gases in reaction compartment 205; Now, because amount of reactant gases remains constant at reaction compartment 205.With Fig. 6 be contrast time, its correlation values is as follows: the pressure in reaction compartment 205 be 5atm and temperature is 590 DEG C time, in the heat treatment furnace in the present embodiment, associated gas density is: average gas density is 2.35kg/m ³, nitrogen (N ₂) gas density is 1.78kg/m ³, Selenium hydride (H ₂se) gas density is 0.57kg/m ³.

Again as shown in Figure 7, owing to being be 2.35kg/m at average gas density ³under react, now the pressure-controlling in gas flow space 204 can be 2.35kg/m being greater than average gas density by controlling organization 50 ³the situation under operate.Under high gas density, comparatively prior heat treatment stove is fast also can to make speed of reaction.Can find out by Fig. 7, the time completing selenylation reaction in reaction compartment 205 only needs about 20 minutes; Similarly, reaction compartment 205 while that its temperature-fall period being also in inner furnace body 20 and the gas flow space 204 of furnace body outer wall pass into the nitrogen of cooling, and inner furnace body 20 furnace wall does not have thermograde doubt, can strengthen air input, same less than the 2hr time, namely to complete cooling action; When Open valve, because reaction compartment 205 contacts with air, thus density at being promoted to 25 DEG C general density of air be 1.184kg/m ³.

Because the present invention can gas production volume density measurement mode control reaction, after measuring reaction compartment 205 in advance via first sensor 103 and the second sensor 203 and measuring the gas density in gas flow space 204, again measuring value is reached controlling organization 50 by signal transmission line, carried out controlling (namely controlling the gas density value of the gas density value in gas flow space 204 slightly larger than reaction compartment 205) according to the gas density difference in reaction compartment 205 and gas flow space 204 by controlling organization 50, the reaction in reaction compartment 205 is carried out smoothly.Therefore thermal reaction furnace 1 of the present invention is in the process be rapidly heated, do not need to carry out pressure release action, and selenylation reaction can be carried out under high gas density due to thermal reaction furnace structure of the present invention; Example: 2.35kg/m ³; Therefore can effectively accelerated reaction carry out, the reaction times is shortened; Such as, in the present embodiment, the reaction times is about 20min; In addition, another advantage of the present invention is temperature-fall period, and about only needing 120min to be namely down to design temperature is 50 ~ 60 DEG C.Clearly, according to the 6th figure, thermal reaction furnace 1 of the present invention, except shortening except the time of selenylation reaction, can also shorten the time of cooling significantly, therefore can accelerate the rate of utilization of thermal reaction furnace 1, and then obviously reduces the cost manufactured.

Similarly, also the first sensor 103 be configured in the gas flow space 204 of Fig. 2 and Fig. 5 can be chosen as a pressure warning unit, and the second sensor 203 be configured in reaction compartment 205 is chosen as a densometer; Equally also can via densometer or pressure measurement measured value, after being sent to controlling organization 50 via signal delivery conduit equally, suitably allotment can be done for the air input of gas flow space 204 and reaction compartment 205, therefore thermal reaction furnace of the present invention, visual actually operating situation decides to be control with pressure-controlling or density domination.

Above detailed description, the thin-film solar cell substrate 3 being all the copper-indium-gallium-selenium compound layer (CIGS) of selenylation reaction is example; But treatment furnace structure of the present invention can also be used in other technique, an another example of lifting illustrates: during to manufacture the thin-film solar cells of copper-zinc-tin-sulfur (CZTS), can add hydrogen sulfide (H equally ₂s) gas and copper (Cu), zinc (Zn), Sn (tin) react, and generate copper-zinc-tin-sulfur film solar cell in heat treatment furnace of the present invention.

Refer again to Fig. 8, is a kind of embodiment schematic diagram with the multistage treatment furnace structure that multiple heat treatment furnace is connected into of the present invention.As shown in Figure 8, because multistage treatment furnace structure 3 body of heater of the present invention is level design, what make multistage treatment furnace structure 3 has both ends open (i.e. an external furnace body 10 has the second side 102 of first side 101 and relative first side 101); When by the series connection of two heat treatment furnaces 1 together time (being connected with the second side 102 of second external furnace body 10 by the first side 101 of first external furnace body 10), and via obturator 80; Such as: the gas-tight ring that elastomeric material is formed; The first side 101 between two heat treatment furnaces and second side 102 is made to form air tight contact, therefore after the 3rd side 201 of of the inner furnace body 20 of two heat treatment furnaces is connected with the four side 202 of of another inner furnace body 20, multistage treatment furnace structure 3 can be completed.Will emphasize at this, the structure of each heat treatment furnace in multistage treatment furnace structure 3 is identical with the treatment furnace structure 1 of the 2nd figure, and its detailed configuration no longer describes in detail.

When two heat treatment furnaces completing series connection are with after forming multistage treatment furnace structure 3, respectively configure openable first gate 1001 and another openable second gate 1002 further in the two ends of multistage treatment furnace structure 3, when the first gate 1001 and the second gate 1002 are closed, by the first airtight construction 10011 and the second airtight construction 10021, the first side 101 of heat treatment furnace and second side 102 are closed, simultaneously, first airtight construction 10011 is via three side 201 airtight joint of gas seal member 10014 with inner furnace body 20, and the second airtight construction 10021 is also via four side 202 airtight joint of gas seal member 10014 with inner furnace body 20, make the gas flow space 204 (the gas flow space serial connection by two heat treatment furnaces forms) between external furnace body 10 inner side-wall 12 and inner furnace body 20 outer side wall 21, and two separate space that reaction compartment 205 (the reaction compartment serial connection by two heat treatment furnaces forms) each self-forming between inner furnace body 20 inner side-wall 22 does not communicate.

In addition, the present invention can also configure heat insulation material further on the inner side-wall 12 of the external furnace body 10 of multistage treatment furnace structure 3, makes to carry out in heat-processed, if can not be passed to the outer side wall 11 of external furnace body 10; And this heat insulation material can be the high temperature resistant material such as quartz brick or mica brick.

In addition, in multistage treatment furnace structure 3, be configured with heating arrangements 30, be fixedly arranged on inner furnace body 20 outer side wall 21, and contact with inner furnace body 20 outer side wall 21; Simultaneously, multistage treatment furnace structure 3 is also configured with gas supply mechanism 40, be configured at the outside of external furnace body 10, be connected with a side of external furnace body 10 and a side of inner furnace body 20 through multiple gas piping, therefore gas can be provided in gas flow space 204 and reaction compartment 205; And controlling organization 50 is configured again in multistage treatment furnace structure 3, be configured at the outside of external furnace body 10 and be connected with the pipeline in gas supply mechanism 40, in order to provide gas to deliver to gas flow space 204 and the amount in reaction compartment 205, and accurately can control gas and form one first pressure (P in the fluid-space 204 ₁), and form one second pressure (P in reaction compartment 205 ₂); Or make gas have the first density in the fluid-space 204, and there is in reaction compartment 205 performance characteristic of the second density.Similarly, in multistage treatment furnace structure of the present invention, in the process of carrying out selenylation reaction, the first pressure (P of gas flow space 204 can be controlled by controlling organization 50 ₁) be greater than the second pressure (P of reaction compartment 205 all the time ₂); Or the first density controlling gas flow space 204 is greater than the second density of reaction compartment 205 all the time.Because embodiment (the i.e. treatment furnace structure 1) distributing style between external furnace body 10 and inner furnace body 20 shown in the present embodiment with Fig. 2 is identical, therefore the various safe design of the aforesaid embodiment to treatment furnace structure 1, be all applicable to the present embodiment; Such as: configure at least one safety valve 70 between the two further in the gas flow space 204 of multistage treatment furnace structure 3 and reaction compartment 205; Do not repeat them here.

Clearly, multistage treatment furnace structure of the present invention and known technology one of do not exist together, be that heat treatment furnace of the present invention need not configure gas piping passage and signal transmission line paths on the first gate 1001, therefore heat treatment furnace of the present invention is in charging and discharging process, the unlatching of the first gate 1001 or closedown, all can not on the structural strength affecting gas supply mechanism 40, therefore except increasing except the reliability for the treatment of furnace structure, the gas piping that can also reduce gas supply mechanism 40 produces the work peace doubt of gas leakage, can be easier when can make thermal reaction furnace structure fabrication simultaneously.Moreover the multistage treatment furnace structure 3 combined via multiple heat treatment furnace, effectively can save equipment cost and more can increase productivity effect.

The foregoing is only preferred embodiment of the present invention, and be not used to limit and of the present inventionly apply for a patent right; Simultaneously above description, should understand and implement for those skilled in the art, and therefore other equivalence completed under not departing from disclosed spirit changes or modifies, and all should be included in the right of application.

Claims

1. the treatment furnace structure that supplied gas reaction uses in manufacturing process of thin film solar battery, comprising:

One external furnace body, there is the second side of a first side and this first side relatively, described first side is identical with described second side bore, and installing one can open the first gate on this first side, on this second side, install one can open the second gate, and the inner side of this first gate configuration one first airtight construction, and the inner side of this second gate configuration one second airtight construction;

One inner furnace body, there is an outer side wall and an inner side-wall, compartment of terrain is fixedly arranged on the inside of this external furnace body, make to form a gas flow space between this outer side wall of this inner furnace body and this external furnace body, and a reaction compartment is formed in this inner furnace body inner side-wall, this inner furnace body has the four side of one the 3rd side and the 3rd side relatively, described 3rd side is identical with described four side bore, when this first gate closes, this first airtight construction engages airtightly with the 3rd side, when this second gate closes, this second airtight construction engages airtightly with this four side, make this gas flow space and each self-forming of this reaction compartment independently airtight space,

One controlling organization, be configured at the outside of this external furnace body, there is provided this first gas and this second gas to the amount in this gas flow space and this reaction compartment in order to control this gas supply mechanism, namely no longer supply after this second gas reaches an amount of reactant gases, and make the fluid-space form one first pressure (P ₁), and reaction compartment forms one second pressure (P ₂), described first pressure is greater than described second pressure, and described first pressure and described second pressure are all greater than the pressure outside described external furnace body.

2. treatment furnace structure according to claim 1, wherein, the material of this external furnace body is for select by following composition: stainless steel SUS304, SUS316.

3. treatment furnace structure according to claim 1, wherein, the material of this inner furnace body is silicon-dioxide.

4. treatment furnace structure according to claim 1, wherein, on a side of this first airtight construction and the 3rd side air tight contact, and this second airtight construction with on a side of this four side air tight contact, each self-forming one silicon dioxide layer.

5. treatment furnace structure according to claim 1, wherein, is configured with at least one first sensor in this gas flow space, and each this first sensor is connected with this controlling organization.

6. treatment furnace structure according to claim 5, wherein, is configured with at least one second sensor in this reaction compartment, and each this second sensor is connected with this controlling organization.

7. treatment furnace structure according to claim 6, wherein, this first sensor and this second sensor are pressure warning unit.

8. treatment furnace structure according to claim 6, wherein, this first sensor and this second sensor are densometer.

9. treatment furnace structure according to claim 1, wherein, this heating arrangements is for select by following combination: graphite heater, halogen lamp.

10. the treatment furnace structure that supplied gas reaction uses in manufacturing process of thin film solar battery, comprising:

One controlling organization, there is provided this first gas and this second gas to the amount in this gas flow space and this reaction compartment in order to control this gas supply mechanism respectively, namely no longer supply after this second gas reaches an amount of reactant gases, and make the fluid-space form one first pressure (P1), and reaction compartment forms one second pressure (P2), described first pressure is greater than described second pressure, and described first pressure and described second pressure are all greater than the pressure outside described external furnace body.

11. 1 kinds for the treatment of furnace structure that supplied gas reaction uses in manufacturing process of thin film solar battery, comprising:

One controlling organization, be configured at the outside of this external furnace body, there is provided this first gas and this second gas to the amount in this gas flow space and this reaction compartment in order to control this gas supply mechanism respectively, namely no longer supply after this second gas reaches an amount of reactant gases, and make the fluid-space form one first pressure (P1), and reaction compartment forms one second pressure (P2), described first pressure is greater than described second pressure, and described first pressure and described second pressure are all greater than the pressure outside described external furnace body.

12. treatment furnace structure according to claim 10 or 11, wherein, the material of this external furnace body is for select by following composition: stainless steel SUS304, SUS316.

13. treatment furnace structure according to claim 10 or 11, wherein, the material of this inner furnace body is silicon-dioxide.

14. treatment furnace structure according to claim 10 or 11, wherein, on a side of this first airtight construction and the 3rd side air tight contact, form a silicon dioxide layer.

15. treatment furnace structure according to claim 10 or 11, wherein, be configured with at least one first sensor in this gas flow space, and each this first sensor are connected with this controlling organization.

16. treatment furnace structure according to claim 15, wherein, are configured with at least one second sensor in this reaction compartment, and each this second sensor is connected with this controlling organization.

17. treatment furnace structure according to claim 16, wherein, this first sensor and this second sensor are pressure warning unit.

18. treatment furnace structure according to claim 16, wherein, this first sensor and this second sensor are densometer.

19. treatment furnace structure according to claim 10 or 11, wherein, this heating arrangements is for select by following combination: graphite heater, halogen lamp.

20. 1 kinds of multistage heat treatment furnaces that supplied gas reaction uses in manufacturing process of thin film solar battery, be connected in series by multiple heat treatment furnace and formed, wherein, each treatment furnace structure comprises:

21. treatment furnace structure according to claim 20, wherein, the material of this external furnace body is for select by following composition: stainless steel SUS304, SUS316.

22. treatment furnace structure according to claim 20, wherein, the material of this inner furnace body is silicon-dioxide.

23. treatment furnace structure according to claim 20, wherein, on a side of this first airtight construction and the 3rd side air tight contact, form a silicon dioxide layer.

24. treatment furnace structure according to claim 20, wherein, this gas flow space is configured with at least one first sensor, and each this first sensor is connected with this controlling organization.

25. treatment furnace structure according to claim 24, wherein, are configured with at least one second sensor in this reaction compartment, and each this second sensor is connected with this controlling organization.

26. treatment furnace structure according to claim 20, wherein, this heating arrangements is for select by following combination: graphite heater, halogen lamp.