A method of treating a sample of aluminium-containing material

Abstract: A post-etch treatment method is provided which is capable of imparting high corrosion prevention performance to aluminum-containing wiring films. The sample of aluminum-containing wiring material that is etched using the halogen-type gas is treated with the plasma of a gas that has an oxygen component, and the resist formed on the aluminum-containing wiring material is reacted with oxygen and is removed. Further, a plasma is generated using a gas having a hydrogen component or this gas is liquefied into droplets thereof on the sample surface, so that halogen components (Cl, Br, etc.) adhered to the aluminum-­ containing wiring material through the etching treatment are reacted with hydrogen and are effectively removed in the form of hydrogen chloride (HCl) or hydrogen bromide (HBr).

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a method of treating samples, and particularly to a method of treating samples adapted to corrosion prevention treatment of aluminum-containing wiring materials after they have been subjected to the etching treatment. Description of the Prior Art According to a conventional method of treating aluminum-containing wiring materials as disclosed in, for example, Japanese Patent Publication No.41766/1983, a semiconductor wafer on which an aluminum-copper alloy film is formed is set in a reactive sputter-etching apparatus, the aluminum-copper alloy film is patterned using a plasma of such a gas as BCℓ 3 , CCℓ 4 , PCℓ 3 , BBr 3 or the like, a hydrogen plasma is generated in the same apparatus, and the patterned aluminum-copper alloy film is exposed to the hydrogen plasma so as to be anti-corrosion treated. In the above conventional technology, however, no attention has been given to removing residual or adhered matter after the etching treatment. In carrying out the etching treatment, in general, the aluminum-containing wiring material (hereinafter referred to as "wiring film") is masked with a photoresist or the like. The wiring film, in this case, may be aluminum-containing films (Aℓ, Aℓ-Si, Aℓ-Cu, Aℓ-Si-Cu, etc.) and laminated wiring films such as aluminum-containing film + barrier metal, cap metal, reflection-preventing film + aluminum-containing film + barrier metal. (The barrier metal is composed of TiW, TiN or the like, and is provided between the silicon substrate and the aluminum-containing film, in order to prevent defective junction due to mutual diffusion of the silicon substrate and the aluminum-containing film and to prevent the wiring resistance from increasing due to the precipitation of silicon in the aluminum-containing film. The cap metal is composed of TiW, TiN, MoSi, or the like, and is used as the uppermost layer of the wiring film of a laminated structure, or is used as the reflection-preventing film. The reflection-preventing film is formed on the aluminum film to suppress the reflection of light at the time of exposure, so that there is formed a resist pattern faithful to the mask.) The etching treatment is effected to treat the wafer on which the wiring film is formed using the plasma of a single gas of the type of halogen such as BCℓ 3 , Cℓ 2 , CCℓ 4 , SiCℓ 4 , HBr, BBr 3 or the like, or a mixture gas thereof. The etching treatment is usually the one that is called reactive ion etching. With the reactive ion etching, the wiring film is etched maintaining a pattern faithful to the mask due to the interaction of radicals and ions in the plasma of the halogen-type gas, and the wiring pattern is obtained. On the thus etched wiring pattern remains a photoresist (hereinafter referred to as "resist") which is a masking material. Halogen components in the plasma adhere on the surface of the resist during the etching and halogen components are implanted due to the bombardment of ions. On the side wall of the etched wiring pattern are adhered the halogen components during the etching or the resist components sputtered by the bombardment of ions. Moreover, aluminum component of the once etched wiring film adhere on the side walls again thereby to form a layer that is called side wall. This layer consists of such components as aluminum, chlorine, carbon, hydrogen, etc. that are adhered in a random fashion. According to the above-mentioned conventional technology, a hydrogen plasma is generated in the apparatus after the etching treatment, and the patterned aluminum-copper film is exposed to the hydrogen plasma so that the aluminum-copper alloy film is anticorrosion-treated. In the treatment with hydrogen plasma, the halogen components adhered to the surfaces between the resist and the wiring pattern or adhered to the portions very close to these surfaces, undergo the reaction with hydrogen in the hydrogen plasma and can be removed as hydrogen chloride (HCℓ) or hydrogen bromide (HBr). However, the halogen components remaining in the resist and in the side walls are not allowed to come in contact with the hydrogen plasma and cannot be removed. Therefore, corrosion easily takes place in the wiring film due to the local battery action between the wiring film materials (between different metals) of the laminated structure or due to halogen components in the side wall (hereinafter referred to as "residual adhered matter"). Japanese Patent Laid-Open No.43132/1987 can be cited as a prior art related to the present invention. This prior art discloses a method of plasma treatment to remove organic film (resist) on the silicon substrate in the plasma of an oxygen gas obtained by adding a compound containing at least carbon or oxygen to the oxygen, e.g., by adding methanol (CH 3 OH) to the oxygen. According to this prior art, the rate of removing resist is increased (relative to the treatment using the oxygen gas plasma) and damage is prevented owing to the treatment with the plasma of a gas obtained by adding methanol (CH 3 OH) to the oxygen (O 2 ). However, this prior art is quite silent about the prevention of corrosion of the wiring film (aluminum-containing wiring material). According to another prior art disclosed in Japanese Patent Publication No. 30268/1987, the aluminum film or the aluminum alloy film is etched using a halogen compound gas, and is then subjected to the anticorrosion treatment using the plasma of a mixture gas consisting of fluorocarbon (CF 4 ) and oxygen (O 2 ) without taking the aluminum film or the aluminum alloy film out of the container. EP-A-247603 describes processes combining stripping of a resist on a patterned aluminium alloy wiring layer using an atmosphere containing a reactive species, for example a plasma of CF 4 and O 2 or a plasma of N 2 and O 2 , and a heating step which effects removal of residual chlorine components resulting from etching in chlorine. The stripping and heating steps may be combined. CHF 3 is described as an alternative fluorinated gas for the stripping. IBM Technical Disclosure Bulletin Vol. 24, No. 113 (April 1982) describes a plasma corrosion inhibition process for treatment of a semiconductor product to remove residual chlorine, by inserting the product into a plasma process chamber and exposing it to a plasma with forming gas (hydrogen/nitrogen). EP-A-140201 describes dry-etching and cleaning treatment using fluorinated ethers. Among such ethers are some containing oxygen and hydrogen atoms. The prevention or removal of corrosion products of aluminium etching with chlorohydrocarbon is mentioned. SUMMARY OF THE INVENTION The object of the present invention is to provide a method of treating samples which is capable of imparting high corrosion preventing performance to the aluminum-containing wiring materials. The present invention is set out in claim 1. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view illustrating an embodiment of an apparatus with which the present invention is put into practice; Fig. 2 is a vertical section view of a sample treatment apparatus as viewed from the line A-A in Fig. 1; Figs. 3, 5 and 6 are diagrams illustrating the procedure of treatment using the apparatus of Fig. 1; Fig. 4 is a diagram showing residual quantity of chlorine which shows the effect of corrosion prevention treatment according to the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS [Examples] Embodiments of the present invention will be described in conjunction with Figs. 1 to 6. Fig. 1 shows a continuously treating apparatus which is capable of continuously carrying out the etching treatment and the post-etch treatment under vacuum condition. A buffer chamber 3 defines space from load lock chambers 4, 9 through an etching chamber 6 up to a post-etch treatment chamber 8. Here, each of the buffer chamber 3, load lock chambers 4, 9, etching chamber 6, and post-etch treatment chamber 8 can be independently partitioned by air-tight means and can be evacuated by an exhaust device (not shown). A load-side cassette 1 is disposed to be opposed to the load lock chamber 4, and a go-straight arm 2 is arranged therebetween. An unload-side cassette 11 is disposed to be opposed to the load lock chamber 9, and a go-straight arm 10 is arranged therebetween. In this apparatus, the process flows as described below. First, a sample (wafer in this case) that is to be treated is introduced into the load lock chamber 4 which is open to the atmosphere from the load-side cassette 1 by the go-straight arm 2. Thereafter, the load lock chamber 4 is air-tightly closed and is evacuated by the vacuum device from the condition of atmospheric pressure to a vacuum condition. Then, the load lock chamber 4, the buffer chamber 3, and the etching chamber 6 are communicated with each other, and the sample is carried by a swing arm 5 into the etching chamber 6 evacuated into a vacuum condition via the buffer chamber 3 that is also evacuated into a vacuum condition. Thereafter, the etching chamber 6 is air-tightly closed to carry out a predetermined etching treatment therein. After the etching treatment is finished, the etching chamber 6, buffer chamber 3 and post-etch treatment chamber 8 are communicated with each other, and the sample is carried by a swing arm 7 into the post-etch treatment chamber 8 that is evacuated into a vacuum condition via the buffer chamber 3 that is evacuated into a vacuum condition. Thereafter, the post-etch treatment chamber 8 is air-tightly sealed to carry out a predetermined post-etch treatment therein. After the post-etch treatment is finished, the post-etch treatment chamber 8, the buffer chamber 3 and the load lock chamber 9 are communicated with each other, and the sample is carried by the swing arm 7 into the load lock chamber 9 that is evacuated into a vacuum condition via the buffer chamber 3 that has been evacuated to the vacuum condition. Then, the load lock chamber 9 is air-tightly closed, and a leakage gas such as N 2 gas is introduced into the load lock chamber 9 to elevate the pressure up to the atmospheric pressure. Then, the load lock chamber 9 is opened, and the treated sample is delivered from the load lock chamber 9 by the go-straight arm 10 and is stored in the unload-side cassette 11 to complete a series of treatments. Fig. 2 is a vertical section view of the sample treatment apparatus illustrating the portion of the post-etch treatment chamber 8 of Fig. 1. Over the post-etch treatment chamber 8 is provided a plasma generating chamber 17 that is partitioned by an aluminum porous plate 18. The upper opening of the plasma generating chamber 17 is closed by a window 19 of quartz, and a microwave waveguide 20 having a microwave oscillator 21 at the end is mounted on the opening. The plasma generating chamber 17 is provided with a gas feed port 22 to which is connected a gas feed pipe 23 to feed a treatment gas into the plasma generating chamber 17 from a gas feed source (not shown) via flow rate control valves 24 and 25. The post-etch treatment chamber 8 is provided with an exhaust port 12 to which is connected a vacuum device (not shown) via a pressure control valve 13 to evacuate the interior of the post-etch treatment chamber 8. The post-etch treatment chamber 8 is further provided with a sample plate 14 on which a sample 16 is placed being opposed to the plasma generating chamber 17. The sample plate 14 is equipped with a heating device 15 for heating the sample 16. In the thus constituted sample treatment apparatus, the microwaves of a frequency of, in this case, 2.45 GHz generated by the microwave oscillator 21 are guided into the plasma generating chamber 17 propagating through the microwave waveguide 20 and the window 19. The microwaves introduced into the plasma generating chamber 17 excite the treatment gas that is introduced into the plasma generating chamber 17. Then, a plasma is generated in the plasma generating chamber 17. The aluminum porous plate 18 provided between the plasma generating chamber 17 and the post-etch treatment chamber 8 reflects the microwaves so as not to enter into the post-etch treatment chamber 8, and prevents the generation of plasma in the post-etch treatment chamber 8. The plasma and chiefly radical components in the plasma generating chamber 17 that has passed through the porous plate 18 is guided onto the sample 16 carried by the exhaust stream of the post-etch treatment chamber 8. Using the continuous treatment apparatus shown in Figs. 1 and 2, the treatment is carired out according to the procedure shown in Fig. 3. In the etching chamber 6, first, the sample 16 on which the wiring film (aluminum-containing wiring material) is formed is etched using a halogen-type gas. The etching treatment is carried out by using an RIE apparatus or a microwave apparatus. Described below is a case of the etching treatment carried out using, for example, a microwave etching apparatus in the presence of magnetic field wherein the sample to be treated is placed on the sample plate, a plasma of the treatment gas is formed by the action of electric field of the microwaves and magnetic field of the solenoid coil, and the sample is etched by the application of a high-frequency bias. In this case, the sample 16 on which the wiring film is formed is obtained by forming a heat oxidized film (SiO 2 ) maintaining a thickness of 600nm on the silicon substrate, and then forming a TiN film, an Aℓ-Si (1%) - Cu (0.5%) film, and TiN film thereon maintaining thicknesses of 100nm, 700nm and 50nm, respectively, and then forming a resist film thereon maintaining a thickness of 1800nm. Further, the wiring pattern is formed in the resist film which is used as a mask for etching. Further, a mixture gas consisting of BCℓ 3 (60cc/min.) and Cℓ 2 (90cc/min.) is used as the halogen-type gas. The etching treatment is carried out under the conditions of a pressure of 2.1 Pa, microwave current of 300mA, and high-frequency electric power of 90 watts. After the etching treatment of the sample 16, there remain components that cause the sample 16 to corrode due to the reasons mentioned in the foregoing prior art. That is, the resist which is a masking material remains on the wiring pattern that is formed by etching, and halogen which, in this case, is chlorine component remains in the resist and on the surface of the resist. Further, the residual adhered matter consisting of aluminum, chlorine, carbon, hydrogen, etc. remains on the side walls of the wiring pattern. Next, the sample 16 on which the resist and residual adhered matter remain is sent to the post-etch treatment chamber 8 to effect the post-etch treatment which is carried out as described below. That is, the flow rates of an oxygen gas (O 2 ) and a methanol gas (CH 3 OH) containing hydrogen component are adjusted by the flow rate control valves 24 and 25, and these gases are mixed together and are introduced into the plasma generating chamber 17. In this case, for instance, the flow rate of oxygen gas is 400cc/min., the flow rate of methanol gas is 80cc/min., and the pressure in the post-etch treatment chamber 8 is 160 Pa. Next, the microwaves are introduced into the plasma generating chamber 17 from the microwave oscillator 21. For instance, the microwave output in this case is 400mA. Then, a plasma of hydrogen component (H), oxygen component (O) and other components is generated in the plasma generating chamber 17. In this case, the plasma consisting chiefly of radicals is guided into the post-etch treatment chamber 8 accompanying the evacuating exhaust stream. Radicals are chiefly comprised of hydrogen and oxygen. The hydrogen radicals react with the chlorine component (Cℓ) in the residual adhered matter (Aℓ, Cℓ, C, H, etc.) to form hydrogen chloride (HCℓ) which volatilizes or forms H 2 O to dissolve the elute chlorine component contributing presumably to removing residual chlorine component that is a cause of corrosion to the wiring film. Further, the oxygen radicals react with the resist to form CO and CO 2 that volatilize, so that the organic components composed chiefly of resist are removed. Thus, the wiring film after the etching treatment is treated using the plasma of the treatment gas consisting of a mixture of methanol gas and oxygen gas, and whereby the resist and the residual adhered matter remaining on the sample are removed and, further, the chlorine components remaining on the surface and inside the sample which cause corrosion are removed. This makes it possible to obtain corrosion prevention performance of longer than 24 hours even in a clean room environment. Since the treatment is carried out while removing the resist, the ashing treatment can be effected at the same time. At this moment, the sample plate 14 is heated by the heating device 15 to heat the sample that is being treated with plasma. Therefore, the chemical reaction of the residual adhered matter or the resist with the radicals is assisted to more efficiently remove the residual matter (residual adhered matter and resist) after the etching treatment. As concrete examples of treatment, described below in conjunction with Fig. 4 are the conventional post-etch treatment and the post-etch treatment of this embodiment in comparison with each other using an aluminum film as the wiring film. Fig. 4 is a diagram showing the residual chlorine quantity reducing effect according to this embodiment. The treatment A of Fig. 4 shows the residual chlorine quantity of the case when the treatment is effected for two minutes in a customary manner using the plasma of a mixture gas consisting of oxygen (O 2 ) and carbon tetrafluoride (CF 4 ). The treatment B shows the residual chlorine quantity of the case when the treatment is effected for one minute using a mixture gas consisting of methanol (CH 3 OH) and oxygen (O 2 ). In the treatment B, the additional treatment is effected for one minute using the plasma of oxygen to prevent the resist from remaining after the treatment using the mixture gas. The sample is an aluminum-film wafer with a 6-inch wiring pattern, the aluminum film having a thickness of 800nm. The treatment A is carried out under the conditions of an oxygen flow rate of 400cc/min, a carbon tetrafluoride flow rate of 20cc/min and a treatment pressure of 160 Pa. The treatment B is first carried out under the conditions of a methanol flow rate of 80cc.min, an oxygen flow rate of 400cc/min and a treatment pressure of 160 Pa., and is then carried out under the conditions of an oxygen flow rate of 400cc/min and a treatment pressure of 160 Pa. The treatment B is carried out while setting the sample plate temperature at 250°C such that the resist ashing rate becomes nearly equal to the values of when a mixture gas of oxygen and carbon tetrafluoride is used. The sample plate 14 should be set at a temperature of 200°C to 350°C from the relationship of the ashing rate of the resist and the thermal damage to the aluminum film. As shown in Fig. 4, the treatment with the plasma of a gas containing hydrogen and oxygen according to this embodiment makes it possible to decrease the residual chlorine content to less than about one-half compared with that of the prior art. Therefore, the corrosion prevention performance of longer than 24 hours to obtained even under clean room environment. As described above, it is better to reliably remove the resist by effecting the additional treatment with the plasma of an oxygen gas after the treatment with the plasma of a gas containing hydrogen component and oxygen component such as methanol or with the plasma of a mixture gas of methanol or the like and oxygen. When the residual adhered matter and resist can be removed by the treatment with the plasma of a mixture gas of methanol or the like and oxygen, however, the additional treatment with the plasma of oxygen need not be carried out. In the aforementioned treatment procedure, the methanol gas and the oxygen gas are mixed together to produce a plasma, in order to carry out the corrosion prevention treatment and the ashing treatment simultaneously. As shown in Figs. 5 and 6, however, it is also allowable to divide this step into treatment with two gas plasmas by changing the treatment gas, i.e., to divide this step into the corrosion prevention treatment and the ashing treatment which are carried out after the etching treatment. According to the procedure of treatment shown in Fig. 5, the resist component (C, H, etc.) is removed (ashing treatment) with the plasma of oxygen gas (O 2 ) after the etching treatment. Then, the treatment gas is changed, and the residual matter (resist component, etc.) and the chlorine component are removed (corrosion prevention treatment) with the plasma of, in this case, the treatment gas of a mixture of oxygen gas (O 2 ) and methanol gas (CH 3 OH). The treatment gas used for the plasma corrosion prevention treatment may be a mixture of (i) any one methanol (CH 3 OH), ethanol (C 2 H 5 OH), acetone (CH 3 COCH 3 ), hydrogen (H 2 ), methane (CH 4 ), and (ii) any one of oxygen (O 2 ), O 3 and N 2 O. By using a gas having oxygen component, the effect for removing the residual matter can be expected. According to this embodiment, as described above, the chlorine quantity remaining in the wiring film after the etching treatment can be greatly reduced compared with that of the prior art, and high corrosion prevention performance is imparted to the wiring film after the etching treatment. The apparatus in the post-etch treatment portion in this embodiment is constituted by providing the porous plate 18 between the plasma generating chamber 17 and the post-etch treatment chamber 8 as shown in Fig. 2. It is, however, also allowable to directly treat the sample 16 with the plasma generated in the plasma generating chamber 17 without employing the porous plate. Further, the plasma is generated using microwaves. It is, however, also allowable to employ an RIE apparatus of the type of parallel flat plates using high-frequency electric power or any other system using high-frequency electric power such as a cylindrical-type apparatus, provided it is capable of generating plasma that contains hydrogen component and oxygen component. In this embodiment, furthermore, the etching treatment and the post-etch treatment are incorporated in the same apparatus as shown in Fig. 1 and are continuously carried out. The invention, however, is in no way limited thereto only. That is, when the resist and the residual adhered matter are to be removed simultaneously, the subsequent additional treatment with the plasma of oxygen may be carried out in a separate treatment chamber which is provided on the outside of the apparatus that is shown in Fig. 1. The widely known ashing treatment with the plasma of mixture gas of oxygen gas and fluorine-type gas may be carried out after the plasma treatment (corrosion prevention treatment) that uses methanol or the mixture gas of methanol and oxygen, and that is effected after the etching treatment. Therefore, when the silicon-type material is used as the resist material component, the residual adhered matter and the resist that stay on the wiring film after the etching treatment can be effectively removed to accomplish high corrosion prevention performance. In the ashing treatment using the plasma of a mixture gas of oxygen and fluorine-type gas, furthermore, the sample plate should be maintained at a temperature of lower than 50°C when the sample 17 is composed of a barrier metal in order to prevent side etching of TiN film or TiW film that lies under the wiring film.

Claims: A method of treating a sample having an aluminium-containing material with a patterned resist, comprising the steps of: (i) etching said sample by means of a plasma having a chlorine component which by the etching generates residual adhered materials containing chlorine, aluminium, carbon and hydrogen; and (ii) after step (i), performing a corrosion-prevention treatment by means of a second plasma containing radicals which are chiefly hydrogen and oxygen radicals, said second plasma being such that both said hydrogen and oxygen radicals react with said residual adhered materials so as to remove them. A method according to claim 1 wherein in step (ii) simultaneously said resist and said corrosive material are removed from the aluminium-containing material by means of said second plasma which is effective to achieve such simultaneous removal. A method according to claim 1 or claim 2, wherein said second plasma is a plasma of a mixture of (i) any one of methanol (CH 3 OH), ethanol (C 2 H 5 OH), acetone (CH 3 COCH 3 ), hydrogen (H 2 ) and methane (CH 4 ), and (ii) any one of oxygen (O 2 ), O 3 and N 2 O. A method according to any one of claims 1 to 3 including an additional treatment using a plasma of oxygen, after step (ii). A method according to any one of claims 1 to 4 wherein said second plasma is generated using microwaves. A method according to claim 5, wherein said second plasma is generated using microwaves of a power of 200W to 4KW at a pressure of 0.4 to 2 Torr.

Inventors: FUKUYAMA RYOOJI, KAKEHI YUTAKA, KAWAHARA HIRONOBU, KAWARAYA AKIRA, NAWATA MAKOTO, SATO YOSHIAKI, SATO YOSHIE, TORII YOSHIMI, FUKUYAMA, RYOOJI, KAKEHI, YUTAKA, KAWAHARA, HIRONOBU, KAWARAYA, AKIRA, NAWATA, MAKOTO, SATO, YOSHIE, TORII, YOSHIMI
Applicants: HITACHI LTD, HITACHI, LTD.
Application year: 1990
Main classification: H01L21
IPC codes: H01L21, C23F4