Background technology
At microelectronics technology, adopt e-beam direct write lithography processing to have nano level high-resolution graphic structure, it is the important means of nanometer processing, its principle is: the macromolecular material in the photoresist material is subjected to the bombardment generation chain rupture (positive glue) or the crosslinked reactions such as (negative glue) of high-power electron beam, solubility property in developing solution changes, the dissolution rate of exposure area and unexposed area is created a difference, it is slower than the zone that has than small molecular weight to have the regional dissolution rate of larger molecular weight, rapidly-soluble regional photoresist material is dissolved to be fallen, the slower regional photoresist material of dissolution rate is retained, thereby plays anti-etching effect in subsequent etching technology.In order to produce the nanometer level superfine figure with electron beam lithography, the photoresist material that use properties is good is very necessary.ZEP520 is the comparatively general photoresist material of current application, and it is the very good positive glue of amplification non-chemically of a kind of performance, rate height respectively not only, and also highly sensitive, anti-etching performance is good; Shortcoming is relatively poor with the adhesivity of semiconducter substrate (especially GaAs material), itself also is easy to generate crackle, crackle and exposure figure weave in can destroy figure, even do not overlap with exposure figure, after over etching and other figure transfer technology, crackle also can be transferred in the lump, and this all can expose and produce serious detrimentally affect.
Generally adopt at present the way that before resist coating, forms adhesion layer earlier to solve the problem of poor adhesion, the effect of adhesion layer is to play the base catalysis reaction at semiconductor substrate surface, the free hydroxyl of transfer of semiconductor substrate surface, the adhesivity of raising photoresist material and semiconductor substrate surface.Normally,, when finishing the gas injection technology that contains HMDS, organic silica-based (trimethyl silicon based: (CH3) such as hexamethyldisilazane (HMDS) etc. at the adhesion layer of semiconductor substrate surface gas deposition a part layer
3Near the dangling bonds of the Siliciumatom that exists in Si-) and in the silicon nitride film near surface or the semiconductor substrate surface carry out following reaction:
The steady state of acquisition aspect chemical energy.In this way, the quantity of the dangling bonds of Siliciumatom reduces in a large number, can suppress by the moisture in the atmosphere thus.
Application number is that 00131453 Chinese patent application discloses a kind of one deck HMDS adhesion layer that formed as toughener before forming low dielectric coefficient medium layer, increases the bonding force between photoresist layer and the semiconducter substrate.But HMDS gas is crystallization easily under differing temps, drops on and can cause exposure not in place on the semiconducter substrate, the unclean problem of etching.The unexposed terms of settlement of above-mentioned patent application.Be illustrated with reference to the accompanying drawings.With reference to shown in Figure 1, be the HMDS deposition apparatus of prior art, described HMDS deposition apparatus comprises container 12, HMDS liquid is housed in the described container and is connected with current-carrying gas 1 by conduit 11; Coating machine 14 is placed with semiconducter substrate 15 in the described coating machine 14, and described coating machine 14 is used for forming the HMDS crystallization on semiconducter substrate 15; Gas passage 13 is used for container 12 is connected with coating machine 14.
Described current-carrying gas 1 is such as in the HMDS liquid that feeds for nitrogen in the container 12, because the pressure effect of current-carrying gas, produce HMDS gas 16 in the container 12, described HMDS gas 16 is by in the 13 input coating machines 14 of gas passage, be sprayed on semiconducter substrate 15 surfaces, also be provided with valve 2 on the described gas passage 13, described valve 2 is used for the conducting of pilot-gas path 13 and closes.In the process of HMDS gas 16 through semiconducter substrate 15 surfaces of gas passage 13 input coating machines 14, because the temperature of each part of gas passage 13 is different, cause HMDS gas 16 to solidify crystallization easily, the crystallisate of these HMDS is delivered to semiconducter substrate 15 surfaces by gas passage 13, cause the exposure of semiconducter substrate 15 surfacial patterns not in place, cause the sordid problem of subsequent etching.
Provide deposition HMDS electronic scanning Electronic Speculum (SEM) test result of semiconducter substrate 15 surface crystallization things afterwards with reference to Fig. 2 A and Fig. 2 B, have difform HMDS crystallisate on semiconducter substrate 15 surfaces as can be seen.
Solidify crystallisation problems in order to solve HMDS, prior art increases the HMDS crystallisate that strainer 3 filters generation on gas passage 13, device as shown in Figure 3, behind the spraying HMDS, the model that adopts day company of this TV station section (KLA-Tencor) is the crystallisate quantity that the surface test instrument of SP1 has been tested semiconducter substrate 15 surfaces, the result as shown in Figure 4, the A post represents to spray the HMDS crystallisate quantity on semiconducter substrate 15 surfaces before among the figure, the B post represents to spray the HMDS quantity of semiconducter substrate 15 surface crystallization things afterwards, as can be seen, after spraying HMDS technology, semiconducter substrate 15 surface crystallization thing quantity with the spraying before compare, maximum increases by 6.7 times, show that adopting strainer to filter HMDS crystallisate technique effect does not gather effect, needs a kind of effective control HMDS crystalline method for this reason.
Embodiment
Essence of the present invention is that the gas passage of HMDS gas process is a constant temperature when forming the HMDS adhesion enhancer on semiconducter substrate, and described homothermic temperature range is 18 to 25 ℃, and the temperature head of described constant temperature sleeve pipe difference is for being no more than 6 ℃.
Below describe specific embodiment in detail by the foundation accompanying drawing, above-mentioned purpose and advantage of the present invention will be clearer:
Deposition device for hexamethyl disilylamine of the present invention has at first provided a kind of embodiment of gas passage, and described gas passage temperature maintenance is constant.
Provide the cross-sectional view of the gas passage 51 of deposition device for hexamethyl disilylamine of the present invention with reference to Fig. 5 A.As shown in the figure, described gas passage 51 peripheries are with constant temperature sleeve pipe 52, and described constant temperature sleeve pipe 52 is made up of inside and outside wall, is full of recirculated water between the inside and outside wall, and described recirculated water is controlled its temperature by the temperature regulator in the external world.Described temperature regulator comprises water recirculator, water recirculator power source, controller, dish power source and leakage sensor, and the constant temperature sleeve pipe links to each other with water recirculator.
Fig. 5 B provides the cross-sectional view of the another kind of gas passage 53 of deposition device for hexamethyl disilylamine of the present invention, and as shown in the figure, described gas passage 53 peripheries are wound with resistance wire, and the temperature regulator by the external world carries out heating and cooling control to resistance wire.
Deposition device for hexamethyl disilylamine of the present invention comprises: container, be equipped with HMDS liquid and be connected with current-carrying gas in the described container; Coating machine is placed with semiconducter substrate in the described coating machine, is used for forming on semiconducter substrate the HMDS layer; The gas passage is used for container is linked to each other with coating machine, and described gas passage is provided with strainer, is used to filter the HMDS crystallisate; The temperature head that partly do not exist together between the strainer of described gas passage and the coating machine interface is no more than 6 ℃, and described temperature range is 18 to 25 ℃.
With reference to Fig. 6, described HMDS deposition apparatus comprises container 611, HMDS liquid is housed in the described container 611 and is connected with current-carrying gas 613 by conduit 612, the temperature range of described container 611 is 22.8 to 23.2 ℃, and described current-carrying gas 613 can be gases such as nitrogen, argon gas, helium.As an optimisation technique scheme of the present invention, adopt nitrogen as current-carrying gas, described nitrogen gas pressure is 30KPa, can be by the amount of the HMDS gas of generation in the flow rate control container 611 of regulating current-carrying gas; Coating machine 631 is placed with semiconducter substrate 632 in the described coating machine 631, and described coating machine 631 is used for forming the HMDS layer on semiconducter substrate 632; Gas passage 621, be used for container 611 is connected with coating machine 14, described gas passage 621 is provided with strainer 623, described strainer 623 is used to filter the HMDS crystallisate that produces in gas passage 621, also be provided with control valve 622 on the gas passage 621, described control valve 622 is used for the conducting of pilot-gas path 621 and closes, and described control valve 622 is on the gas passage 621 between strainer 623 and the container 611.The temperature difference that partly do not exist together between the strainer 623 of described gas passage 621 and coating machine 631 interfaces is no more than 6 ℃, and the temperature of described gas passage 621 is 18 to 25 ℃.
In the HMDS liquid that current-carrying gas 613 feeds in the container 611, because the pressure effect of current-carrying gas 613 produces HMDS gas in the container 611, described HMDS gas is sprayed on semiconducter substrate 632 surfaces by in the 621 input coating machines 631 of gas passage.
The temperature range of described gas passage 621 is 18 to 25 ℃, is no more than 6 ℃ by the difference temperature head of controlling constant temperature sleeve pipe 621.Satisfy above-mentioned condition and can keep constant temperature by the thermostat device that adds, such as by 621 periphery puts homothermic constant temperature sleeve pipe 624 in the gas passage, in described constant temperature sleeve pipe 624 has, outer wall, in the described constant temperature telescopic, be full of the constant temperature circulating liquid between the outer wall, described liquid can be oil, water etc., optimize embodiment as one of the present invention, described liquid is recirculated water, described constant temperature sleeve pipe 624 is enclosed within the outer wall of gas passage 621, coverage be strainer 623 from the gas passage to the gas passage 621 with the interface of coating machine 631, described constant temperature sleeve pipe 624 links to each other with temperature regulator 641, and described temperature regulator 641 is used to control the circulation and the temperature of liquid in the constant temperature sleeve pipe 624.The temperature regulator 641 that the present invention adopts is that (TokyoElectron, model Ltd) is the temperature regulator (Multi Thermo-conUnit) of INR-244-254*-*** in Tokyo Electronics Co., Ltd..
Described temperature regulator 641 comprises circulator 642, circulator power supply 643, controller 644, power supply 645 and leak sensor 646.
Described circulator 642 links to each other with constant temperature sleeve pipe 624, is used for making that by inner unidirectional flow pump the liquid circulation of circulator 642 is extremely outside, and the control signal that receives controller 644 is simultaneously adjusted flow rate of liquid and temperature.
Described circulator power supply 643 is used for providing direct current to circulator 642, adjusts galvanic current by the control signal that receives controller 644.
Described controller 644 is used for to the circulator power supply 843 adjustment galvanic current that transmits control signal; Be used for sending signals such as liquid circulation velocity, fluid temperature to circulator 642; Be used to receive the leakage signal output alarm of leak sensor 646 and be used for sending the control dc current signals to power supply 645.
Power supply 645 is used to coolship that direct current is provided, by receiving the control signal control galvanic current of controller 644.
Leak sensor 646 is used to survey leakage liquid stream and sends a signal to controller 644, and leak sensor 646 is provided with photodiode (LEDs) lamp, and the bright expression of green light is normal, and the bright expression of red light is unusual.
Described temperature regulator 641 is connected by interconnecting device with the junction C of constant temperature sleeve pipe 624, and described interconnecting device is present technique field personnel's known technology, does not give unnecessary details at this.
Be placed with semiconducter substrate 632 in the described coating machine 631, described semiconducter substrate 632 is silicon or is gallium arsenide that be sent in the coating machine as HMDS gas 633, MDS gas 633 and semiconducter substrate generation chemical reaction are silicon such as semiconducter substrate 632:
Semiconducter substrate 632 surfaces have a Si-OH key, when covering one deck HMDS, described HMDS and hydroxyl react and generate the hydrophobic molecular layer.After the silylation, semiconducter substrate 632 surface coverage have " Si-(CH
3)
3", change semiconducter substrate 632 surface polarity purposes thereby reach.
The present invention gives the deposition method embodiment that employing HMDS deposition apparatus as shown in Figure 6 carries out HMDS.
At first in container 611, produce HMDS gas 633, in the described container 611 conduit 612 is set, current-carrying gas is fed in the HMDS liquid in the containers 611 by conduit 612, feed the intravital pressure effect of HMDS liquid by current-carrying gas, the easier volatilization of HMDS liquid makes HMDS gas more be easy to generate.Described current-carrying gas can as an optimisation technique scheme of the present invention, adopt nitrogen as current-carrying gas for gases such as nitrogen, argon gas, helium, feeds in the container 611 by conduit 612.
Container 611 is provided with the through hole (not shown), conduit 612 is connected by a through hole with container 611, one end of gas passage 621 is connected by another through hole with container 611, the other end of gas passage 621 links to each other with coating machine 631 simultaneously, except plugging in conduit 612 and gas passage 621 through holes, container 611 rest parts are all airtight, to prevent that the HMDS gas leakage is to container.
Also be provided with valve 622 and strainer 623 on gas passage 621, the folding that described valve 622 is used to be used for to gas passage 621 is controlled; Described strainer 623 is used for the HMDS solid crystal things that produce in the gas passage 621 are filtered, and semiconducter substrate 632 surfaces in coating machine 631 prevent to drop.
The temperature difference that partly do not exist together between the strainer of described gas passage and the coating machine interface is no more than 6 ℃, and the temperature of described gas passage is 18 to 25 ℃.Satisfy above-mentioned condition, can be by 621 periphery puts homothermic constant temperature sleeve pipe 624 in the gas passage, in described constant temperature sleeve pipe 624 has, outer wall, in the described constant temperature telescopic, be full of the constant temperature circulating liquid between the outer wall, described liquid can be oil, can be water, optimize embodiment as one of the present invention, described liquid is water, described constant temperature sleeve pipe 624 is enclosed within the outer wall of gas passage 621, coverage be from the gas passage 621 strainer 623 up in the distance gas passage 621 with the interface of coating machine 631, described constant temperature sleeve pipe 624 links to each other with temperature regulator 64, and described temperature regulator is used to control the circulation and the temperature of liquid in the constant temperature sleeve pipe 624.The temperature regulator 641 that the present invention adopts is that (Tokyo Electron, model Ltd) is the temperature regulator (Multi Thermo-con Unit) of INR-244-254*-*** in Tokyo Electronics Co., Ltd..
Described temperature regulator 641 comprises circulator 642, circulator power supply 643, controller 644, power supply 645 and leak sensor 646.
Described circulator 642 links to each other with constant temperature sleeve pipe 624, is used for making that by inner unidirectional flow pump the liquid circulation of circulator 642 is extremely outside, and the control signal that receives controller 644 is simultaneously adjusted flow rate of liquid and temperature.
Described circulator power supply 643 is used for providing direct current to circulator, adjusts galvanic current by the control signal that receives controller 644.
Described controller 644 is used for to the circulator power supply 843 adjustment galvanic current that transmits control signal; Be used for sending signals such as liquid circulation velocity, fluid temperature to circulator 642; Be used to receive the leakage signal output alarm of leak sensor 646 and be used for sending the control dc current signals to power supply 645.
Power supply 645 is used to coolship that direct current is provided, by receiving the control signal control galvanic current of controller 644.
Leak sensor 646 is used to survey leakage liquid stream and sends a signal to controller 644, and leak sensor 646 is provided with photodiode (LEDs) lamp, and the bright expression of green light is normal, and the bright expression of red light is unusual.
Described temperature regulator 641 is connected by interconnecting device with the junction C of constant temperature sleeve pipe 624, and described interconnecting device is present technique field personnel's known technology, does not give unnecessary details at this.
After the temperature control by above-mentioned constant temperature sleeve pipe 624, any two places of 621 tube walls are no more than 6 ℃ such as the temperature head at A place among the figure and B place in the gas passage.
The other end of gas passage 621 links to each other with coating machine 631, be placed with semiconducter substrate 632 in the described coating machine 631, described semiconducter substrate 632 is silicon or is gallium arsenide, gas passage 621 feeds the HMDS gas 633 that produces in the container 611 in the coating machine 631, be sent in the coating machine as HMDS gas 633, because semiconductor substrate surface covers hydroxyl " OH " group, HMDS gas can be solidificated in semiconducter substrate 632 and semiconducter substrate 632 surface hydroxyl generation chemical reactions, is silicon such as semiconducter substrate 632:
Semiconducter substrate 632 surfaces have a Si-OH key, when covering one deck HMDS, described HMDS and hydroxyl react and generate the hydrophobic molecular layer.After the silylation, semiconducter substrate 632 surface coverage have " Si-(CH
3)
3", change semiconductor substrate surface polarity purpose thereby reach.
Based on the crystallisate of semiconductor substrate surface that adopted day surface test instrument Equipment Inspection of the SP1 model of company of this TV station section (KLA-Tencor) behind the above process implementing, test result as shown in Figure 7, as shown in Figure 7, tested respectively in the gas passage is under the different constant temperatures and the crystallisate on the surface of the semiconducter substrate that do not have (to add *) under the constant temperature, gas passage A place's temperature and gas passage B place temperature are any difference temperature in gas passage (as shown in Figure 6) among Fig. 7, add * and represent the gas passage not keep the constant temperature temperature that do not exist together.When the gas passage temperature is constant temperature, the difference of A place, gas passage and gas passage B place temperature is less than 5.0 ℃, on semiconducter substrate, do not find to have crystallisate, when the gas passage temperature is not set at constant temperature, A place, gas passage and gas passage B place temperature differ by more than 6 ℃, occur the solid crystal thing of HMDS on semiconducter substrate.The result shows thus, and whether the crystallization of HMDS gas has relation with the temperature head that the gas passage does not exist together, and result of the present invention shows that also by keeping the gas passage be the crystallization that constant temperature can be controlled HMDS gas well.
Though oneself discloses the present invention as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art without departing from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.