METHOD FOR INCREASING THE RESISTANCE OF A SOLID MATERIAL SURFACE AGAINST ETCHING

Abstract: A method for increasing the resistance of a solid material surface against etching. It comprises the step of subjecting the surface to a chemical treatment which may be in a plasma, a liquid or a vapour containing reactive species that, reacting with the material (2) to be protected, form a thin native layer (5) that is highly resistant to an etchant subsequently applied. Described is a fabrication process of a chromium mask for use in integrated circuit manufacturing. Initially, a glass plate (1) coated with a chromium film (2) is provided. After photoresist application (3), exposure to an e-beam pattern (4) and development the plate is subjected to a CF₄ + O₂ plasma treatment thereby forming a thin CrF₂ layer (5) on the chromium surface. This layer is shaped in accordance with the desired mask pattern. It is resistant against the chromium etch solution applied in a later process step.

Description: METHOD FOR INCREASING THE RESISTANCE OF A SOLID MATERIAL SURFACE AGAINST ETCHING The invention concerns a manifacturing process involving a method for increasing the resistance of a solid material surface against etching. It may, for example, be employed in the process of fabricating masks for use in integrated circuit manifacturing. Etch processes are widely used. A particularly important application is in the manifacturing of semiconductor and Josephson junction devices or integrated circuits. In combination with photolithographic processes they can be employed to pattern a structure, e.g., by selectively etching zones of a metal film thereby leaving the desired pattern on the substrate supporting the film. A more specific application is in the fabrication of metal masks that are in turn used in photolithographic processes. In order to achieve selective etching numerous methods have been developed such as those that employ photoresist stencils for pattern definition. These methods are well known in the art. More recently, a basically different process has been proposed in European Patent Application No. 002 1095 which provides for image reversal and is particularly useful in the fabrication of low-coverage patterns. This process includes ;in additional step by which a metal coating is applied to the surface regions of the metal film that are to form the desired pattern, i.e., regions that are not to be etched off in a subsequent etching step. This latter process, involving the deposition of a non-native etch resistant metal layer on the surface of the metal film by an evaporation process, becomes critical, however, for high density patterns with line width below 1 pm and accurate pattern edge definition that are required in today's highly advanced integrated circuit techniques. In order to obtain defect-free patterns a pin-hole free coverage of the underlying film is needed. This calls for a thickness of the deposited layer of several hundred i which results in less accurate pattern edge definition since it impedes subsequent lift-off of the deposite required in the process. As explained above, this method, furthermore, requires additional process steps. The metal layer is to be deposited and, after removal from the vacuum chamber, a lift-off operation is needed that becomes increasingly critical with increasing thickness of the deposited metal layer. The invention is intended to remedy these drawbacks. The proposed method is characterized in that the surface of the material, the etch rate of which is to be decreased, is subjected to a chemical treatment by which a native reactive surface layer is formed that is highly resistant to a subsequently applied etchant. The main advantage offered by the invention is that the method permits the fabrication of high precision patterns with accurate edge definition. The process is, furthermore, simple in that the chemical treatment and the subsequent resist removal step can take place in the same vacuum. Furthermore, the new method is notcritical in that process parameters can reliably be controlled to avoid attacking of the photoresist stencils as well as undesirable etching of the material to be covered by the native surface layer. Other parameters, such as process temperature, are non-detrimental to the structures produced. The method also permits image reversal especially of interest for low coverage patterns where the e-beam writing time can be substantially reduced when high resolution positive photoresists are used. The inventive method can advantageously be used in the fabrication of metal masks. Such masks, consisting of a patterned metal film supported by a glass substrate, are being used in the photolithographic steps employed in the fabrication of, e.g., semiconductor or Josephson junction devices and, more particular, in the fabrication of integrated circuits. One way of carrying out the invention is described in detail below with reference to drawings which represent only one specific embodiment and in which Fig. 1 A through E illustrate the process steps involved in the production of a metal mask. Briefly, the mask fabrication process in accordance with the invention involves the following steps: initially a glass plate coated with a metal film is provided. After application of a positive high resolution photoresist, the resist is exposed, e.g., by an e-beam .rit- ing the desired mask pattern, and developed. Subsequntlv the exposed resist is removed in a conventional manner. Then the plate is subjected to a gas discharge plasma treatment during which a thin nativesurface layer is formed at the surface of the exposed metal film. This layer is highly etch resistant against the metal etchant later on used during the process after the remaining resist has been removed. Contrary to conventional photo resist techniques, the process leads to an image reversal. The resulting metal film pattern corresponds to the light or e-beam pattern to which the photoresist-covered plate is exposed whereas conventional techniques result in metal patterns corresponding to the zones that had not been exposed. When e-beam techniques are used in high precision applications, the image reversal method substantially reduces the required e-beam writing time for low coverage patterns that are frequently needed in electronic device applications. With the aid of the figures the inventive method will now be described in more detail. Fig. 1A shows a glas substrate 1 coated with a thin chromium film 2 that is to be patterned. This film has a thickness of at least 300 A, preferably 500 to 1'000 i. A photoresist layer 3 is applied in a conventional manner on top of the metal film 2. A positive resist is used such as Shipley AZ-1350 (Trademark of Shipley Company, Inc.). The photoresist is then exposed to an e-beam pattern, a section of which is illustrated by the arrows 4. Optical methods may of course also be employed to expose the photoresist to the desired pattern. After removal of the exposed resist the structure shown in Fig. 1B is obtained. The substrate is then placed into a conventional plasma etching' chamber where it is exposed to a CF4 plasma treatment, the plasma con taining approx. SOb 02.2With the following process para- meters the plasma treatment has yielded the desired formation of the native surface layer: pressure - 500 m Torr, 2 RF power - 0,4 /cm , RF voltage - 280 V peak to peak, temperature - 20 C, duration of plasma treatment - at least 20 minutes. During the plasma treatment a thin reactive CrF2 layer 5, shown in Fig. 1C, is formed on the chromium film. It is a native layer, i.e., a chemical compound with the chromium and the reactive species of the plasma, in this case fluorine, as constituents. The remaining photoresist is then stripped off. This results in the structure of Fig. 1 D with the region of the chromium film that corresponds to the pattern written by the e-beam 4 covered by the reactive surface layer 5. This# layer proved to be very resistant against the etchant used in the next process step during which the chromium is etched in regions 6. The etch solution used: CH3COOH + Ce (NH4)2(NO3)6 in deion. H2O In this solution it takes typically 0,5 minutes to etch through 300 R of unprotected chromium. It has been observed that the etch resistant layer 5 obtained by the plasma treatment described above causes an etch "incubation" time of 3 to 4 minutes, i.e., chromium film 2 is protected for this period of time before it is being etched at approx. the normal etch rate. The etch time ratio of approx. , is sufficiently high to guarantee selective etching and thus high contrast chromium patterns. After etching for about 2 minutes the structure shown in Fig. 1 E is obtained. The processing conditions during the chemical treatment must be such that the material of film 2 is not etched off and that no surplus material deposition takes place. Also, the photoresist mask must not be effected by the treatment. The above described process meets these requirements completely satisfactorily. The application of the inventive method is by no means restricted to the specific materials and process conditions used in the example. The material on which the etch resistant layer is to be formed may consist of metals other than chromium such as aluminum, copper, silver, or it could be nonmetallic, e.g., a semiconductor material. The main qualification for the material being that during the chemical treatment a reactive native layer is formed that is etch resistant. Equally, the chemical treatment applicable is not restricted to the CF4 plasma process described above. The treatment can also be in a liquid or in a vapour. For a plasma treatment the reactive species can be nitrogen, carbon, fluorine, chlorium, oxygen - these materials being cited only as examples. The species chosen, together with the material the surface of which is to be made etch resistant, must form the desired native layer. With the above described CF4 plasma treatment it has been observed that the etch "incubation" time and thus the resulting resistance against wet chemical etch ing is enhanced by adding a small amount of oxygen to the CF4 plasma. This effect may be explained by the mechanism of the plasma chemistry: the CFX molecules will dissociatively absorb at the chromium surface by forming fluorine and carbon atoms as dissociation products. The fluorine atoms will react with the chromium by forming CrF2. However, the carbon will cover the chromium film as an absorbed layer, impeding further formation of CrF2. The addition of oxygen will result in the formation of CO and CO as volatile products and, in turn, will clean the chromium surface from absorbed carbon. The addition of 2 to the CF4 plasma will thus result in an enhancement of the formation rate of CrF2. It is, however, expected that exposure to a pure (100e) CF4 plasma during an extended period of time will yield the same result. The composition of the native layer naturally depends on the materials and reactive species used. Among others it can be a nitride, carbide, fluoride, chloride, or oxide. A few more specific examples besides the above cited CrF2 are: Al4C3, Air3, CuF, CuF2, AgF. The etchants against which the surface layer provides a protection also depend on the materials and processes used, the earlier mentioned CHJCOOH + (NA4)2(NO3)6 in deion. 142 being an example for a chromium etch solution against which CrF2 is highly resistant. A few other examples of resistant layer-etchant combinations are: Al C is etch resistant against alkali, which may be 43 used to etch Al; AlF is resistant against acids and alkalines; CuF is resistant against acids such as WC1.

Claims: C L A I M S 1. Method for increasing the resistance of a solid material surface against etching characterized in that the surface of the material (2) is subjected to a chemical treatment by which a reactive native sur face layer (5) is formed that is highly resistant to a subsequently applied etchant. 2. Method as claimed in claim 1, characterized in that the chemical treatment is in a liquid, a vapour or in a plasma containing the reactive species required to form the surface layer. 3. Method as claimed in claim 2, characterized in that one or more of the following reactive species are used: nitrogen, carbon, fluor ine, chlorine, oxygen. 4. Method as claimed in claim 3, characterized in that the chemical treatment is in a gas discharge CF4 plasma containing 0 to 10% OXy- gen (02). 5) Method as claimed in claim 1, characterized in that the material (2) the etch re sistance of which is to be increased at the surface consists of a metal. 6j Method as claimed in claim 5, characterized in that the material (2) consists of chromium, aluminum, copper or silver. 7) Method as claimed in claim 1, characterized in that the material (2) the etch re sistance of which is to be increased at the surface consists of a semiconductor. 8) Method as claimed in claim 1, characterized in that the reactive layer (5) con sists of a nitride, carbide, fluoride, chloride or oxide. 9) Method as claimed in claim 4, characterized in that a chromium surface is subject ed to a CF4 + O2 plasma treatment by which a CrF2 layer is formed that is highly resistant to an etch- ing solution CHJCOOH + Ce(NH4)2(NO3)6 in deion. H9 0. 10. Method as claimed in claim 9, characterized in that the plasma pressure is above 150 m Torr.

Inventors: DATWYLER, KURT, OOSENBRUG, ALBERTUS, Dätwyler, Kurt
Applicants: INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1981
Main classification: C23F1
IPC codes: C23C16, C23C8, G03F1, C23F1, G03F7, C23F4, H01L21