CN1309860C - Low-pressure chemical gas phase vapour connecting apparatus and thin film producing method - Google Patents
Low-pressure chemical gas phase vapour connecting apparatus and thin film producing method Download PDFInfo
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- CN1309860C CN1309860C CNB031202608A CN03120260A CN1309860C CN 1309860 C CN1309860 C CN 1309860C CN B031202608 A CNB031202608 A CN B031202608A CN 03120260 A CN03120260 A CN 03120260A CN 1309860 C CN1309860 C CN 1309860C
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Abstract
一种低压化学气相沉积装置，包括：容纳作为原料的金属化合物的容体、通过对该容体加热使有机金属化合物气化从而生成原料气体的加热装置、容纳析出薄膜的基板的反应器、使反应器处于低压氛围的排气泵、对来自于反应器的使用过的原料气体进行冷却的冷槽，其特征在于，所述冷槽在使用过的原料流动的流道内具有蜂窝结构的筒体。本发明的薄膜制造方法使用上述低压化学气相沉积装置。
A low-pressure chemical vapor deposition device, comprising: a container for containing a metal compound as a raw material, a heating device for generating a raw material gas by heating the container to vaporize an organic metal compound, a reactor for containing a substrate for depositing a thin film, and the reactor An exhaust pump in a low-pressure atmosphere, and a cold tank for cooling the used raw material gas from the reactor, characterized in that the cold tank has a honeycomb structure cylinder in the flow channel where the used raw material flows. The thin film manufacturing method of the present invention uses the above-mentioned low-pressure chemical vapor deposition apparatus.
Description
Technical field
The present invention relates to a kind of device and film-forming method that utilizes Low Pressure Chemical Vapor Deposition to carry out metallic film or metal compound film manufacturing.
Background technology
Because chemical Vapor deposition process (Chemical Vapor Deposition method: hereinafter to be referred as the CVD method) can be made uniform epithelium, have ladder and cover energy (step coverage) good advantage, so, be in the general film formation technology of using in the manufacturing of membrane electrode of semiconductor device.
The film formation process of this CVD method is, with material gasification, be delivered to substrate surface after, the raw material particle of conveying reacts on substrate, piles up.Especially in recent years, consider the reduction of temperature of reaction and thin film fabrication efficiently, be fit to use the Low Pressure Chemical Vapor Deposition (hereinafter to be referred as the LPCVD method) that in the atmosphere of low pressure, on substrate, reacts.In addition, in order to reduce temperature of reaction, the metallic compound that uses as raw material also can utilize organometallic compound.
Here, the apparatus for manufacturing thin film as the LPCVD method generally comprises: hold the appearance body as the metallic compound of raw material; Make organometallic compound be gasificated as the heating unit of unstripped gas by holding the body heating; Hold the reactor that makes the substrate that film separates out, these machines are connected by pipe arrangement.In the LPCVD device, be provided with the off-gas pump that makes reactor be low pressure atmosphere, and, be provided with the liquid trap (cold trap) that the condensation composition in the exhaust is removed.
But, present inventors etc. consider the rising of the low thin film fabrication cost that causes of starting compound utilising efficiency of CVD method, developed reacted used raw material has been reclaimed, refining goes out the unreacted metal compound the used raw material after reclaiming, makes the regeneration techniques (opening the 2001-342566 communique with reference to the spy) that becomes recycling state.Present inventors etc. think that utilization is suitable as the liquid trap of the retrieving arrangement of this used raw material.This is because utilize liquid trap that used raw material is reclaimed easily.Promptly, the starting compound of CVD method (organometallic compound) boiling point is low, vapor pressure is low, under more cryogenic situation from gas to undergoing phase transition of liquid, easily condensation, so consider that from the original purpose of liquid trap liquid trap also is good machine as retrieving arrangement.In addition, this is because in the above-mentioned LPCVD subtraction unit, be typically provided with liquid trap, so needn't the machine that reclaim usefulness specially be set because of it is utilized.
In such regeneration techniques,, preferably can reclaim more used raw material certainly for the more metallic compound of regenerating.
Summary of the invention
For this reason, the present invention is to be purpose so that a kind of LPCVD device that can reclaim how used raw material to be provided.
The present inventor is in order to address this problem the result who discusses, in order to reclaim used raw material effectively, think the cooling efficiency that is necessary to improve the used raw material in the liquid trap, its concrete grammar is to think that filling solid charges are suitable in the gas flow of liquid trap.General liquid trap, its inwall are effective cooling surface, but in this traditional liquid trap, the contact area of used raw material and cooling surface is little, so can't cool off fully used raw material.To this, filling charges in gas flow increase the contact area of used raw material and cooling surface, thereby bring into play high cooling efficiency.
This charges generally are suitable for the disk shape material of Rasching ring class.In this occasion,, need filling charges to high-density in order to improve the cooling efficiency of used raw material, but filling to high-density charges, the pressure-losses is increased, become pump deflated obstacle, so reduce the decompression rate in the reactor, film formed the straight knot of reaction exert one's influence.Therefore, so general disk shape charges are inapplicable.
For this reason, present inventor etc. think, both otherwise the exhaust efficiency of pump is exerted an influence, can cool off the charges of used raw material again efficiently, the cylindrical shell of honeycomb structure preferably, thus obtained the present invention.
Promptly, LPCVD device of the present invention, have: thus hold the metallic compound that becomes raw material the appearance body, by to this appearance body heating make the organometallic compound gasification generate unstripped gas heating unit, hold the substrate of separating out film reactor, make reactor be in low pressure atmosphere off-gas pump, the used unstripped gas that comes from reactor is carried out the refrigerative cold trap, it is characterized in that, cold trap has the cylindrical shell of honeycomb structure in used raw material mobile runner.
Be applicable to the charges of honeycomb structure of the present invention, have a plurality of holes on its cross section, and this hole connects towards the length direction of charges (used unstripped gas flow direction).Therefore, like this charges of honeycomb structure can not increase the pressure-losses of flowing gas.In addition, the charges of this honeycomb structure are separated by the next door on every side and a large amount of holes are arranged, and have very big surface-area.Therefore, the high charges of cooling efficiency of the unstripped gas that was to use of the charges of this honeycomb structure.
Thus, LPCVD device of the present invention can have the thin film fabrication efficient identical with legacy equipment, and can more effectively reclaim used raw material than legacy equipment with the exhaust efficiency identical with traditional LPCVD device to reducing pressure in the reactor.Like this, renewable a large amount of feed metal compound, thus can reduce the manufacturing cost of film.
Below the charges that are filled in the honeycomb structure in this cold trap are elaborated, this material is metal preferably.Because of metal fever conductivity height, so can cool off used raw material effectively.In addition, the size of charges, length are preferably about 0.01～5.0m.0.01m less than, then can not cool off fully, and surpass 5.0m used raw material, then cooling efficiency is not only had influence, and the large-scale exhaust efficiency that causes of cold trap descends.In addition, the size in the hole of this honeycomb structure, its maximum diameter is preferably about 0.5～30mm.0.5mm below, then the pressure-losses of charges increases, and in addition, the used raw material that produces condensation is sometimes blocked.And surpass 30mm and very roomy when the maximum diameter in hole, then can not cool off fully used raw material.
Below, the structure of the CVD device of having used above-mentioned cold trap is explained.At first, pack into the occasion of CVD device of the cold trap that the present invention is used, the upstream side that is preferably in cold trap is provided with back-flow prevention valve.This is because the organic efficiency of not using raw material of the cold trap that the present invention uses is fine, but is necessary to prevent that the fluid in the cold trap from flowing backwards.
The position that is provided with of cold trap can be at the upstream side of pump, the either side in downstream side.Being arranged on which side can carry out reasonably determining according to the stability of the starting compound of recycle object etc.That is, the starting compound of recycle object stable low has the occasion of decomposing possibility more in early days, and cold trap is arranged on the pump upstream side, can reclaim before compound decomposition.
But, cold trap is arranged on the occasion of pump upstream side, preferably makes to keep its pressure to equate in the cold trap or than carrying out film formation under its slightly little state with reactor pressure.Most of vapor pressures of the employed starting compound of CVD method (organic compound) are low, and are too low as pressing in the cold trap, even then low temperature also is difficult to condensation.For this reason, by the pressure in the cold trap is brought up to a certain degree, just can reclaim effectively.At this moment, the optimum range of pressing in the cold trap is more than the 0.1Pa, below the pressure in reactor.
Here, cold trap is being arranged under the occasion of pump upstream side, as the control gimmick of the pressure in the cold trap, be preferably in and pump between the cold trap pressure regulator valve of regulating the pressure in the cold trap is set, and, be preferably between reactor and the pump bypass pipe be set.Like this, can easily keep pressure in the cold trap to equate or slightly littler than it with pressure in the reactor.That is, in the occasion of pump upstream side configuration cold trap, as not taking any measure, then pressure is much lower in the cold trap inner pressure ratio reactor, but just can regulate in the cold trap and press by the cold trap pressure regulator valve is set.In this structure,, make its interior pressure-controlled in suitable scope by the switching of cold trap pressure regulator valve, and to the exhaust of reactor, by and use bypass pipe, even the cold trap pressure regulator valve is in the state that closes, also reliable exhaust can be proceeded, the interior pressure of reactor can be kept always.Such as, closing presure variable valve when the pressure in the cold trap is lower than required pressure, this moment, the exhaust of reactor was proceeded by bypass pipe, carries out film and form under the environment that the pressure of reactor can not rise.
In addition, the operation that actual film is made generally suspends the CVD device in order to change substrate, utilizes the batch treatment that opens and closes reactor to carry out.At this moment, the switching of each reactor all needs its inner pressure relief, boosts.Here the LPCVD device of Shuo Ming pressure regulator valve with cold trap downstream side and the bypass pipe between reactor and the pump by it is carried out suitable operation, can carry out the thin film fabrication operation effectively.That is, can make pressure regulator valve only be in movable state when thin film fabrication, pressure regulator valve cuts out during substrate exchange, and cold trap is cut off, and keeps decompression state, does not need the exhaust of cold trap amount of capacity during the reactor decompression, can carry out the decompression of reactor effectively.
But, in the LPCVD device, used unstripped gas is directly tied in the inflow pump from reactor when preventing thin film fabrication, and the bypass trip valve that cuts off bypass pipe preferably is set.
Fig. 1 is the explanation of thin film fabrication engineering that said upstream side at pump is here had the LPCVD device of cold trap.The LPCVD device of Fig. 1, its best form are to be provided with the reactor pressure variable valve of the pressure of cold trap pressure regulator valve, bypass pipe, back-flow prevention valve, bypass trip valve and conditioned reaction device.
Among Fig. 1, in when starting device when thin film fabrication (initial), the state that all valves are in out is to reactor, cold trap both sides reduce pressure (Fig. 1 (a)).
Then,, imported unstripped gas and carry out thin film fabrication, but the limit monitored that flanging opens and closes (Fig. 1 (b)) to the cold trap pressure regulator valve in the cold trap this moment when the pressure in the reactor reaches under the state of the specified pressure that is fit to thin film fabrication.In addition, directly tie in the inflow pump from reactor, close the bypass trip valve in order to prevent used unstripped gas.
And this thin film fabrication finishes, and when carrying out the substrate replacing, closes cold trap pressure regulator valve and back-flow prevention valve, behind the cut-out cold trap reactor is boosted.Install the back to the reactor decompression at new substrate, this moment, the cold trap pressure regulator valve also was a closing condition, opened the bypass trip valve, carried out reactor decompression (Fig. 1 (c)) by bypass pipe.But, substrate is changed operation repetition Fig. 1 (b) of each valve of back, the operation of (c).
At above situation, also cold trap can be arranged on the pump downstream side among the present invention.Cold trap is arranged on the occasion in pump downstream side, different with the above-mentioned occasion that is configured in upstream side, machine, pipe arrangements such as cold trap pressure regulator valve and bypass pipe can be set just can improve in the cold trap and press.And, have device and uncomplicated, can be with the advantage that reclaims after the starting compound condensation.This apparatus structure, good stability is effectively for the recovery of decomposing the low starting compound of possibility in the regenerative process.
Description of drawings
Fig. 1 is the figure of the thin film fabrication engineering of expression LPCVD device of the present invention.
Fig. 2 is the synoptic diagram of the LPCVD device of the 1st embodiment use.
Fig. 3 is the synoptic diagram that is applied to the cold trap in the LPCVD device that the 1st embodiment uses.
Fig. 4 is the synoptic diagram of the LPCVD device of the 2nd embodiment use.
Fig. 5 is the synoptic diagram of the employed LPCVD device of Comparative Examples.
Embodiment
Below utilize accompanying drawing that embodiments of the invention are explained.
The 1st embodiment
Fig. 2 is the synoptic diagram of the LPCVD device of present embodiment use.The LPCVD device 1 of Fig. 2 is by as the thermostatic bath 2 of the container of enclosing organometallic compound, reactor 3, to the pump 4 that reduces pressure in the reactor 3 and reacted used unstripped gas is cooled off the cold trap 5 that makes its condensation constitute.Be provided with substrate 6 in the reactor 3 and to the well heater 7 of its heating.
In this LPCVD device 1, be gasificated as unstripped gas at thermostatic bath 2 internal heating, mix, be delivered to the surface of the substrate 6 in the reactor 3 with oxygen 21 as carrier gases as the organometallic compound 20 of raw material.Then, by 6 heating of 7 pairs of substrates of well heater, thereby produce the CVD reaction at substrate surface.In addition, at the cold trap upstream side back-flow prevention valve 8 is set.
Fig. 3 elaborates to this cold trap 5.This cold trap 5, for importing used unstripped gas from its lateral introducing port 100, the form of discharging upward from central part pipe arrangement 101.Be provided with the charges 102 of honeycomb structure in the runner that used unstripped gas is passed through.The material of these honeycomb charges 102 is a stainless steel.In addition, the wall at cold trap has water coolant 103 to flow.
Utilize this LPCVD device 1, carried out the manufacturing of ruthenium film.The condition of this moment is as follows.
Raw material: two (ethyl cyclopentadienyl) rutheniums (200g)
Raw material supplying speed: 0.05g/min
Substrate: the silicon plate of titanizing
Substrate temperature: 300 ℃
Chamber pressure: 133.3Pa (1.0torr)
Carrier gas flow: 50mL/min
Reaction gas flow: 200mL/min
Here, at the wall of cold trap 5, the refrigeration agent (water) that flows on its cooling surface, the gas cooling to 10 that will flow through ℃.
In the test of this thin film fabrication, up to raw material use until exhausted carry out film forming after, when having collected the yield in the cold trap 5, the amount of recovery has 164g, calculating the rate of recovery is 82%.
At 105 ℃, the state of 46.7Pa (0.35torr) is distillation down, is recovered to the 150g cut, is 75% the rate of recovery for the initial stage raw material weight with the amount that reclaims this moment.This cut using gas chromatography is analyzed, found that it is that purity is two (ethyl cyclopentadienyl) rutheniums of 99.56%.
The 2nd embodiment
In the present embodiment, the position that is provided with of cold trap is at the CVD of pump upstream side device.Fig. 4 be the LPCVD device 1 that uses of present embodiment ' synoptic diagram.This LPCVD device 1 ', its basic structure is identical with the 1st embodiment, is made of thermostatic bath 2, reactor 3, cold trap 5, pump 4.But, be provided with cold trap pressure regulator valve 9 between cold trap 5 and the pump 4 in the present embodiment, be connected with the reactor pressure variable valve 10 of conditioned reaction device internal pressure in the downstream of reactor, between the upstream side pipe arrangement of the downstream side of reactor pressure variable valve 10 pipe arrangement and pump 4, be connected with the bypass pipe 12 that two ends are provided with bypass trip valve 11.In addition, the structure of cold trap 5 is identical with the 1st embodiment.
Utilize this LPCVD device 1 ', carried out the manufacturing of ruthenium film.The condition of this moment is identical with the 1st embodiment.But, the limit monitors the pressure limits control cold trap pressure regulator valve 8 in the cold trap 5, makes the identical 133.3Pat of being of pressure (1.0torr) of pressure and reactor 3 in the cold trap.
In the test of this thin film fabrication, up to raw material use until exhausted carry out film forming after, when having collected the yield in the cold trap 4, the amount of recovery has 154g, calculating the rate of recovery is 77%.
In addition, at 105 ℃, the state of 46.7Pa (0.35torr) is distillation down, is recovered to the 142g cut, is 71% the rate of recovery for the initial stage raw material weight with the amount that reclaims this moment.This cut using gas chromatography is analyzed, found that it is that purity is two (ethyl cyclopentadienyl) rutheniums of 99.56%.
Comparative Examples
Fig. 5 is the synoptic diagram of the employed traditional LPCVD device 30 of Comparative Examples.This LPCVD device 30, its basic structure is identical with the LPCVD device 1 of the 2nd embodiment, but the structure difference of cold trap has been used general cold trap 31.In addition, cold trap pressure regulator valve, bypass pipe (bypass trip valve) are not set in this LPCVD device 30.
Use the LPCVD device of this Comparative Examples, under the condition identical, carried out the ruthenium film manufacturing with embodiment.
The cold trap internal pressure of this Comparative Examples is 1.33 * 10
-2Pa.The used raw material that traps in the cold trap is 10g, and its rate of recovery is 5%.This Comparative Examples is compared the rate of recovery with present embodiment extremely low, can think it mainly is because the great cause of cooling efficiency difference in the cold trap, and the pressure in the cold trap of Comparative Examples is too low, and unstripped gas can't produce that enough condensations cause under 10 ℃ of such cooling temperatures.
As mentioned above, the CVD film that utilizes cold trap to reclaim organometallic compound from used raw material of the present invention forms in the engineering the more metallic compound of regenerating.The present invention can improve the thin film fabrication cost of CVD method.
Claims (9)
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| CNB031202608A CN1309860C (en) | 2003-03-06 | 2003-03-06 | Low-pressure chemical gas phase vapour connecting apparatus and thin film producing method |
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| CNB031202608A CN1309860C (en) | 2003-03-06 | 2003-03-06 | Low-pressure chemical gas phase vapour connecting apparatus and thin film producing method |
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| CN1309860C true CN1309860C (en) | 2007-04-11 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06302603A (en) * | 1993-03-26 | 1994-10-28 | Hitachi Ltd | IC element |
| JP3092286B2 (en) * | 1992-01-17 | 2000-09-25 | 株式会社島津製作所 | Thin film internal stress measurement device |
| JP2001181841A (en) * | 1999-12-24 | 2001-07-03 | Kojundo Chem Lab Co Ltd | Method for producing iridium-containing thin film by chemical vapor phase growth method |
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2003
- 2003-03-06 CN CNB031202608A patent/CN1309860C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3092286B2 (en) * | 1992-01-17 | 2000-09-25 | 株式会社島津製作所 | Thin film internal stress measurement device |
| JPH06302603A (en) * | 1993-03-26 | 1994-10-28 | Hitachi Ltd | IC element |
| JP2001181841A (en) * | 1999-12-24 | 2001-07-03 | Kojundo Chem Lab Co Ltd | Method for producing iridium-containing thin film by chemical vapor phase growth method |
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Granted publication date: 20070411 |