Abstract:
A process which allows effective application or removal of materials to and from substrates using a scanning probe microscope operated at atmospheric pressure. 
     The substrate is placed in a trough, located on the x-y table of a scanning probe microscope (SXM), and this trough is filled with a liquid and/or gaseous medium up to a level such that the top side of the substrate is covered with a thin layer, composed of at least one monolayer of the medium. For depositing a structured precipitate from the medium or for structuring etching of the surface of the substrate, the microtip of the SXM is then dipped into the layer and supplied with an electric voltage or with voltage pulses. 
     The process can be used for applying or removing materials to and from substrates. The process is also usable for characterization of the geometry and for restoration or the production of microtips of SXM cantilevers, as well as for storing information, for reading information and for erasing information.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a process for applying or removing materials to and from substrates using a scanning probe microscope (SXM), operated at atmospheric pressure. The SXM which may be a scanning tunneling microscope (STM), a scanning force microscope (SFM) or a scanning near-field microscope (SNOM). 
     RELATED TECHNOLOGY 
     It is known to use scanning tunneling microscopes for lithography. In this case, existing resist layers or metal surfaces in air are illuminated by ions or electrons or are oxidized, and fine structures are thus produced (Matsumoto, M. Ishii, K. Segawa: J. Vac. Sci. Technol. Vol. 14(2), 1331 (1996); E. A. Dobisz, C. R. K. Marrian: Appl. Phys. Lett. 58(22), 2526 (1991)). When there is sufficient water content in the ambient air, that is to say, given a humidity of more than 15%, and depending on the polarity of the tip, the illumination is effected with hydronium or hydroxyl ions (H. W. P. Koops, E. A. Dobisz, J. Urban: J. Vac. Sci. Technol. Vol. 15(4), 1369 (1997); E. A. Dobisz, H. W. P. Koops, F. K. Perkins: Appl. Phys. Lett. 68(22), 3653 (1996); A. R. Anway, Field Ionization of Water, The Journal of Chemical Physics, Vol.50, (1969) 2012-2021). In dry ambient air, illumination with electrons can be achieved. 
     It is also known to use scanning tunneling microscopes for applying material to a substrate. In this case, atoms of the substrate are displaced on the substrate, or the material is applied by transferring probe material by field evaporation (R. Gomer, IBM J. Res. Develop. 30, 428 (1986)). 
     Also known is to use scanning tunneling microscopes for high-resolution structuring processes and for information storage processes (S. C. Minne, Ph. Flueckinger, H. T. Soh, C. F. Quate: J. Vac. Sci. Technol. Vol. 13, 1380 (1995)). 
     It is also known to operate scanning tunneling microscopes for deposition lithography under vacuum conditions. In this case, material is supplied from a Knudsen cell, i.e., a reservoir with constriction of the delivery through a cannula or a nozzle (M. A. McCord, D. P. Kern, T. H. P. Chang: J. Vac. Sci. Technol. Vol. 6, 1877 (1988); E. E. Ehrichs, W. F. Smith, A. L . DeLozanne: Ultramicroscopy 42-44, 1438 (1992)). Organometallic compounds and substrates with unprepared surfaces are used. 
     Furthermore, it is known to carry out the process of electrolysis with an STM or SFM (JP 06 297252 A, JP 05 288714 A). In so doing, the ions contained in a liquid electrolyte are fixed by the electric field to a sample placed in the electrolyte. 
     These prior processes suffer from a number of disadvantages. It is particularly disadvantageous that it is necessary to work under vacuum conditions, which necessitates high expenditure in terms of equipment and time. Also disadvantageous is the fact that the conductivity of the deposits is usually inadequate because of the great carbon content. Since the known procedure is a serial process, the process is a relatively slow one. Furthermore, only small areas, typically 100 μm×100 μm at most, are writable. The high degree of probe wear is also disadvantageous. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide a method which allows effective application or removal of materials to and from substrates using a scanning probe microscope operated at atmospheric pressure. 
     In the method according to the present invention the substrate is placed in a trough, located on the x-y table, of a scanning probe microscope (SXM), which may be a scanning tunneling microscope, a scanning force microscope or a scanning near-field microscope, and the trough is filled with a liquid and/or gaseous medium up to a level such that the top side of the substrate is covered with a thin layer made of at least one monolayer of the medium. For depositing a structured precipitate from the medium or for the structuring etching of the substrate surface, the microtip of the SXM is then dipped into the layer and supplied with an electric voltage or with voltage pulses. 
     According to the invention, organometallic or other inorganic and organic compounds are used as the liquid and/or gaseous medium. 
     The invention present provides for supplying the medium in a quantitatively controlled manner. This may expediently be carried out with the use of weight and density differences existing between the ambient air and the medium, or with the assistance of a pump and controlled valve. 
     In doing this, the air in the trough will form a lower layer in response to the feeding of the gaseous medium which has a greater molecular weight than the air. 
     A thermoelectric sensor array or a reflection interferometer, composed of a light source, beam guide, line detector and evaluation electronics, or a total reflector with linear detector may expediently be used for monitoring the level of the medium. 
     According to the present invention, the medium may be changed during the production of the structured precipitate or during the structuring etching. 
     The etching products produced during the structuring etch removal are expediently transported away from the surface of the substrate by a rinsing medium. 
     For the application or removal of larger structure fields and for the three-dimensional construction of nanostructures with the SXM, according to the invention, one or more SXM probe cantilevers having a plurality of microtips may be used, the simultaneous use of all the microtips being ensured by a resistor built into each microtip or by active current control of the individual microtip. 
     When an SXM probe cantilever having a plurality of microtips is employed, use is also made of a test tip which is utilized as a positioning guide for this SXM probe cantilever during the application or removal of the material, for observation of larger structure fields and/or for three-dimensional processing of nanostructures. 
     According to the present invention, Me 2 Au(tfac) (dimethylgold trifluoroacetylacetonate), Me 2 Au(hfac) (dimethylgold hexafluoroacetylacetonate), Me 2 Au(acac) (dimethylgold acetylacetonate), CpPt (CH 3 ) 3  (cyclopentadienyl platinum trimethyl), Mo(CO) 6  (molybdenum hexacarbonyl), Cu(hfac) 2  (copper dihexafluoroacetylacetonate) may be used as the organometallic compound. 
     The present invention provides for the use of TiI 4  (titaniumiodite) or TiCl 4  (titaniumchloride) as the inorganic compound. 
     In the case of etch removal, XeF 2  (xenondifluoride), TiI 4  (titaniumiodite), TiCl 4  (titaniumchloride), WF 6  (tungstenhexafluoride) or other highly fluorinated or halogenated compounds may be used as the medium. 
     The present invention also relates to the use of the method according to the present invention for characterization of the geometry and restoration or production of microtips of SXM cantilevers, a tip that is electrically contacted to a conductor track being arranged in the trough on a substrate, and with its aid the geometry of the microtip being scanned by scanning microscopy, or with its aid, restoration or production of a microtip being carried out by supplying an electric voltage or voltage pulses to the contacted tip in order to deposit a precipitate from the medium onto the SXM probe cantilever. 
     To this end, the polarity of the bias voltage of the SXM, used when depositing a precipitate on the substrate or when etching the substrate, is simply reversed. This results in a material application or an etching of the microtip of the SXM probe cantilever. The polarity of the bias voltage of the SXM can subsequently be reversed again, to then continue to deposit or etch on the substrate. 
     The present invention also relates to the use of the method according to the present invention to store information, to read information and to erase information, where using the process, molecules or molecular clusters which are suitable as information carriers are applied to the substrates in order to store information, are detected in order to read information, and are removed or restructured in order to erase information. 
     In this case, according to the present invention, a plurality of tips may be used, repaired or else cleaned in the same way, but also in a mutually independent way. 
     In the method according to the present invention, individual gas atoms adsorbed at the surface of the substrate or of the microtip of the SXM are decomposed, caused by the use of the gaseous medium. A portion of them, and specifically metal atoms having carbon residues, are deposited on the surface of the substrate or of the microtip, or an etching of the substrate or of the microtip is carried out. It is virtually about a CVD process (chemical vapor deposition process), while dispensing with the vacuum necessary for the customary CVD by creating a local precursor atmosphere utilizing the particular material property of the precursor (high vapor pressure, greater density than air). 
     In contrast, in the electrolysis process of Japanese Patent Document Nos. JP 06 297252 A and JP 05 288714 A mentioned above, using an STM or SFM, work is done with a liquid medium, namely, an electrolyte. There a completely different process principle than for the CVD of the present invention is employed. While in the case of the electrolysis, the ions contained in the electrolyte are fixed by the electrical field to the substrate, in the method according to the present invention, a deposition induced by electron beam or ion beam is carried out. 
     The method according to the present invention has the particular distinction that it is not necessary to work under costly vacuum conditions. It is also advantageous that highly conductive deposits can be used, and that by rapid changing of the precursors, different processes such as deposition and etching can be carried out in a simple manner one after the other. Another advantage is that the probes which become worn when the process is being carried out can be regenerated again using the same process. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     The present invention is explained in more detail below with reference to exemplary embodiments. The following schematic representations are shown in the associated drawing: 
     FIG. 1 shows the working arrangement in the case of a conventional scanning tunneling microscope; 
     FIG. 2 shows a basic working arrangement for implementing the method according to the present invention, using a scanning probe microscope; 
     FIG. 3 shows arrangements for regulating the level and for changing the media in order to carry out the method according to the present invention with a scanning probe microscope; 
     FIG. 4 shows an arrangement having a plurality of microtips and a test tip for implementing the method according to during deposition or etching on larger structure fields and for the three-dimensional construction of nanostructures; 
     FIG. 5 shows an arrangement for regulating the level and for changing the media in order to carry out the process of the present invention when etching with a scanning probe microscope; and 
     FIG. 6 shows the working arrangement for in-situ repair of a microtip of a scanning probe microscope; 
     FIG. 7 shows a flow chart of the working stages for the characterization of microtips and for the repair of a write-read-erase head of an information storage device that works on the basis of the method according to the present invention. 
    
    
     DETAILED DESCRIPTION 
     The working arrangement, shown in FIG. 1, of a conventional scanning tunneling microscope that is operated at atmospheric pressure, has a probe  1  which can be moved in the x, y and z directions by three piezo motors and which, at its lower end, bears one or more cantilevers  2  having one or more microtips with which it is possible to scan a substrate  3  supported on a substrate holder  4 . Substrate holder  4  is fastened on x-y table  5  that is able to move in the x-y direction. 
     A scanning tunneling microscope of this type is controlled by signal electronics (not shown in the drawing) with an image-memory, and image-reproduction and image-processing systems, as well as with a tip movement system and a sample movement system. The electronics additionally have one or more channels with which the microtips can be guided in accordance with a computer-generated pattern, and various constant or time-variable and pulsed voltages with amplitude and duration tailored to the process can be applied to the various microtips for imaging, coating or etching the substrate. 
     In the working arrangement shown in FIG. 2 for carrying out the process of the present invention, substrate  3  is located on substrate holder  4  in a trough  6  that is fastened on x-y table  5  of a scanning probe microscope. Dimethylgold acetylacetonate, which is composed of heavy organometallic molecules with a molecular weight of 380 and has a low vapor pressure of 40 mTorr, is introduced at atmospheric pressure into trough  6  as medium  7 . The heavy vapor  9  of medium  7  which forms thereby displaces the air (molecular weight O 2 =32) at the bottom of trough  6  and, in the course of time, coats the bottom of trough  6  to a level  8  at which a few monolayers of vapor  9  cover substrate  3 . The microtip of cantilever  2 , with which water ions are emitted, dips into this layer over substrate  3 . The vapor molecules adsorbed on the surface of substrate  3  are broken up by the impact of the ions and, in the case of deposition, a lasting deposit is formed on substrate  3 . 
     In the case of etching, an etching product is created which, through suitable selection of an etching vapor component, is as gaseous as possible so that it can be transported away by a vapor movement. 
     For process control, it may be advantageous to bring substrate  3  and medium  7  to the same temperature or different temperatures. This may advantageously be implemented by heating elements under substrate  3  and with a separately arranged medium reservoir. 
     In order to determine the endpoints of the complete vapor exchange, level measurement of the vapor level is advantageously used. According to FIG. 3, the level can be measured: 
     by measuring the thermal conductivity at miniaturized resistors  15  of a Wheatstone measuring bridge circuit  16  which are applied, at various heights, to the inside of trough  6 ; or 
     for greater precision, with the assistance of a light source  10 , utilizing the total reflection at the transition to the denser medium; or 
     by evaluating the dual-beam interference. 
     Dual-beam interference occurs when light beam  11  emanating from a light source  10  is partially reflected at the vapor layer and partially penetrates into the vapor layer, and is then reflected at the lower edge of the vapor layer, namely, at the bottom of trough  6  or on substrate  3 , and upon emerging, interferes with the light beam reflected at the surface. The interference pattern is formed by superposition of light beams  12 , for example with the aid of a lens  14 , on a detector  13  or screen placed in its focal plane. The thickness of the vapor layer can then be inferred from the intensity profile of the interference pattern. When measuring by total reflection and when evaluating the interference intensity, a line-scanning camera with computer read-out is advantageously used as a spatially-resolving detector  13 . 
     To accelerate the vapor-feed process, it is advantageous—as shown in FIG.  3 —to provide at least one reservoir  19  for the medium on trough  6 . For this purpose, a compensating vapor quantity  20  is conveyed to or from trough  6  via a tube  17  and a valve  18  with the aid of a piston  21  which is actuated in a cylinder  23  by a positioning motor  22 . In this context, the valve setting, the piston position and the temperature of substrate  3  may advantageously be adjusted by computer control. Using this device, or a similar compensating-volume control which, according to FIG. 3, is constructed with a bellows  24  and a positioning motor  22 , the vapor for the deposition or for the etching can be controlled and can be removed and supplied rapidly, and it is also possible to change from one medium  7  to other media  7 . 
     In the arrangement shown in FIG. 4 for carrying out the process on larger structure fields and for three-dimensional construction of nanostructures, a plurality of microtips  29  that can be addressed independently via separate conductor tracks  30  are used. This allows separate driving, for example, in order to achieve a two-dimensional pointwise structured application  31  and etching in writefields on a substrate  28 , with simultaneous guiding by a microtip  26  which is driven in read mode using a conductor track  25  and with which, for example, a predetermined trace  27  is tracked by real-time signal evaluation and position correction. For example, using a square tip array having 100 separately addressable and readable microtips  29  that are arranged in a fixed or variable grid dimension, deposits structured in one position can thus be produced simultaneously. 
     In order to fabricate such microtips using the process of nanolithography with deposition in a particle-beam instrument, separately addressable microtips with 100 nm spacing may be constructed in a line array and even in a square array. Since the ion-emitting microtips are formed from the Taylor cone of water at the end of the presented tip, the presented microtips establish only the location of the deposition by their position. By setting the voltage it is possible, even with microtips that are at the same voltage, to deposit and reproduce the pattern of the distribution of the microtips in question with their spacings. It may sometimes be necessary, for each microtip, to build a resistor that limits the emission current into the base of the microtip in order to make it possible for all the microtips to emit ions uniformly at the same voltage. 
     A tip array fabricated in this manner can advantageously be used for the production of photonic crystals and further lattice-like structures, such as computer-generated holograms. 
     For the storage of information, the limiting frequency of the cantilever at 10 kHz signifies a possible read rate of 1 Mbit/s. If one information unit is deposited in 0.1 ms, then this is also the write rate of the arrangement. At present, 1 ms is required as the deposition time. Therefore, a write rate of 100 Kbit/s can be achieved for the storage of information. 
     Using the process according to the present invention, it is also possible to remove material by etching. This is advantageous for cleaning the substrate surfaces and microtips that are to be coated, as well as for removing materials already deposited. For example, by virtue of the fluorine contained, xenondifluoride etches silicon in response to ion excitation and produces gaseous etching products. 
     An arrangement which is suitable for etching and is operated at atmospheric pressure is shown in FIG.  5 . As a result of a suitable gas-vapor guidance and the use of a further trough  32 , which is connected via a flexible connecting tube  33  to trough  6  of the scanning probe microscope and can be adjusted relative to it in the indicated direction of motion  35 , the etching gas flows through the connecting tube, depending on the difference in level between trough  6  and trough  32 , and thus moves the vapor surrounding the microtip. Consequently, the etching products are moved away from the microtip. The connected compensating piston  34 , with reservoir and valve, makes it possible to supply or remove the etching-gas components in order for the etching process to be terminated and to be carried out with computer control. 
     With this arrangement, which is equipped with a level measurement device (not shown in the drawing) and which can be operated with computer control, it is possible to achieve material transport of the reaction products by vapor flow during the etching of the substrate or the microtips. Besides the aforementioned xenondifluoride vapor, those solid etchants which have a high vapor pressure and contain heavy atoms are also suitable as the etchant. 
     The working arrangement shown in FIG. 6 for in-situ repair of a microtip of a scanning probe microscope shows a presented microtip  39  contacted by a conductor track  38 . Conductor track  38  is located on a substrate holder  36 . Microtip  39  is surrounded by a high-impedance proximity deposit  37  which makes it possible to regulate the highest point of microtip  39 . To produce a new microtip, a working tip  40  is brought to rest over this point and a tip  41  is put on working tip  40  using a short pulse. Using this new tip  41 , microtip  39  is then re-scanned and the process is repeated with a change in the pulse length, the voltage, the vapor pressure and the vapor composition by changing the partial pressure and the material composition of the medium until the desired fine or coarse tip radius has been produced on tip  41 . 
     The process according to the present invention can also be used to store information by depositing molecules and molecular clusters and for erasing information by removing or restructuring molecules with the assistance of a single microtip or by a multitip arrangement. In this case, the microtips are guided locally by an additional test tip. Reading takes place using the same microtip, but at a voltage below the reaction threshold for writing or erasing. The microtip arrangement for the multitip write, read and erase technology can be produced internally by deposition lithography. In addition, the write-read-erase head can be repaired in situ with this process, and it can be routinely tested and repaired in preprogrammed fashion in order to maintain the performance of the write-read-erase memory device. 
     FIG. 7 shows the flow chart for the automatic functional sequence of characterization and repair for a write-read-erase head on a data storage device, which operates on the basis of the process according to the invention. First, an empty trough is provided, as shown in block  102 . Then, the tip is approached to the trough, using STM imaging, as shown in block  104 . The tip is characterized, including assessing the radius and the height, as shown in decision block  106 . If the tip is judged in block  106  to be good, then the process is finished, as shown in block  108 . If the tip is judged in block  106  to be poor, then the process continues with filling the trough with etching gas, as shown in block  110 . The old tip is then etched off, as shown in block  112 . The trough is next emptied of etching gas, as shown in block  114 , and filled with deposition precursor, as shown in block  116 . The tip is positioned according to memory, as shown in block  118 . The tip is constructed with deposition pulses, as shown in block  120 . The trough is then emptied of deposition precursor, as shown in block  122 .