CN103119694A

CN103119694A - Removal of masking material

Info

Publication number: CN103119694A
Application number: CN2010800629333A
Authority: CN
Inventors: 阿里·阿法扎里-阿达卡尼; 托马斯·H·鲍姆; 卡尔·E·博格斯; 埃马纽尔·I·库珀; 道格拉斯·塞沃; 马修·科恩; 马默德·科加斯泰; 罗纳德·W·努内斯; 乔治·加布里尔·托蒂尔
Original assignee: Advanced Technology Materials Inc; International Business Machines Corp
Current assignee: International Business Machines Corp; Entegris Inc
Priority date: 2009-12-11
Filing date: 2010-12-10
Publication date: 2013-05-22
Also published as: EP2510538A4; WO2011072188A3; EP2510538A2; SG181642A1; TW201140254A; JP2013513824A; KR20120108984A; WO2011072188A2

Abstract

Methods for removing a masking material, for example, a photoresist, and electronic devices formed by removing a masking material are presented. For example, a method for removing a masking material includes contacting the masking material with a solution comprising cerium and at least one additional oxidant. The cerium may be comprised in a salt. The salt may be cerium ammonium nitrate. The at least one additional oxidant may be a manganese, ruthenium, and/or osmium-containing compound.

Description

The removal of masking material

Technical field

Present invention relates in general to remove masking material, more specifically, the present invention relates to use the solution removal masking material that comprises cerium.

Background technology

Resist comprises photoresist, is to be used for during semiconductor device is made at upper radiosensitive (for example light radiation the is responsive) material that forms patterned layer of substrate (for example semiconductor crystal wafer).After the substrate with a part of resist-coating is exposed to radiation; the resist (for negative resist) of the resist of exposed portion (for for positive corrosion-resisting agent) or unexposed portion is removed; expose following substrate surface, stay remaining substrate surface by resist-coating and protection.Resist more generally can be called as masking material.Can carry out other manufacturing process on unlapped substrate surface and remaining resist, for example implanted ions, corrosion or deposition.After carrying out other manufacturing process, remove remaining resist in strip operation.

In implanted ions, the accelerated substrate that will implant that approaches of doping ion (for example ion of boron, boron difluoride, arsenic, indium, gallium, phosphorus, germanium, antimony, xenon or bismuth).Ion is implanted in the exposure region and remaining resist of substrate.Implanted ions can be used for for example forming implantation region, for example transistorized channel region and source region and drain region in substrate.Implanted ions also can be used for forming slight doped drain and double diffusion drain region.Yet the ion in the implantation resist can exhaust the hydrogen from the resist surface, causes resist to form skin or shell, and described skin or shell can be the harder carburization zones of lower part (being the main part of resist layer) than resist layer.Outer and main part has different coefficient of thermal expansions, and with different speed, stripping process is reacted.The resist that high dose ion is implanted can cause serious sclerosis or the crust of resist, causes between skin and main part larger difference aspect for example coefficient of thermal expansion, solubility and other chemistry and physical characteristic.

The transistor of one type is called as field-effect transistor (FET).FET is also referred to as metal-oxide semiconductor (MOS) FET(MOSFET), but MOSFET is the misnomer to the FET with Si-gate rather than metal gate.The FET transistor comprises source region, drain region, the channel region between source region and drain region, at the gate insulator on channel region and the gate electrode on gate insulator.In the early stage FET from very early stage technology, gate electrode typically comprises metal.In technology afterwards, gate electrode typically comprises the semiconductor silicon form of polysilicon (for example with).Use silicon is because silicon is compatible with the silicon dioxide that is used as gate insulator, and because silicon can tolerate for making FET and the high temperature that comprises the integrated circuit of FET.Yet some very recent technology reuse metal gate electrode.Metal has advantages of resistance less than polysilicon, thereby has reduced signal propagation time.In addition, in the very recent technology of transistor size less than the size of prior art, must make gate dielectric layer very thin (for example 1 nanometer).Very thin gate dielectric layer can cause the problem that is called as depletion of polysilicon (poly depletion) in polygate electrodes, in this case, when transistorized channel region is reverse, forming depletion layer in the gate polysilicon electrode of gate dielectric.For fear of depletion of polysilicon, need metal gate.Can use the various metals grid material, normally higher with the dielectric constant that is called as high-k dielectric gate insulator material coupling.The example of metal gate material comprises tantalum, tungsten, tantalum nitride and titanium nitride (TiN).

Summary of the invention

Principle of the present invention provides and for example has been used for removing the method for masking material and the device that forms by removing masking material.

According to an aspect of the present invention, method that be used for to remove masking material comprises masking material is contacted with the solution that comprises cerium.

According to a further aspect in the invention, remove masking material by masking material is contacted with the solution that comprises cerium, form electronic device.

According to a further aspect in the invention, be used for comprising from the method that substrate is removed photoresist photoresist is contacted with the solution that comprises cerium.With photoresist with before solution contacts, suppose photoresist by implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than approximately 5000 electron-volts (5KeV).Substrate comprises titanium nitride.

According to another aspect of the invention, by photoresist is removed to form electronic device from substrate.Photoresist removes by described photoresist is contacted with the solution that comprises cerium.With photoresist with before solution contacts, photoresist by implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than about 5KeV.Preferably, electronics nitrogen titanium.

According to a further aspect in the invention, the method that forms electronic device comprises and forms the substrate that comprises titanium nitride, with the photoresist implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than about 5KeV, and photoresist is contacted with the solution that comprises cerium.

In one or more execution modes of the present invention, masking material comprises resist or photoresist, and the solution that is used for removal resist or photoresist comprises ammonium ceric nitrate.

According to an aspect of the present invention, method that be used for to remove masking material comprises masking material is contacted with the solution that comprises cerium and at least a other oxidant.

According to a further aspect in the invention, form electronic device by masking material is contacted the removal masking material with the solution that comprises cerium and at least a other oxidant.

The other one side according to the present invention is used for comprising from the method that substrate is removed photoresist photoresist is contacted with the solution that comprises cerium and at least a other oxidant.With photoresist with before solution contacts, suppose photoresist by implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than approximately 5000 electron-volts (5KeV).Preferably, substrate comprises titanium nitride.

According to another aspect of the invention, by photoresist is removed to form electronic device from substrate.By being contacted with the solution that comprises cerium and at least a other oxidant, photoresist removes photoresist.With photoresist with before solution contacts, photoresist by implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than about 5KeV.Preferably, electronics nitrogen titanium.

According to a further aspect in the invention, the method that forms electronic device comprises and forms the substrate that comprises titanium nitride, with the photoresist implanted ions greater than about 5x10 ¹⁴Ion/square centimeter and/or before ion affects photoresist the average energy of ion greater than about 5KeV, and photoresist is contacted with the solution that comprises cerium and at least a other oxidant.

In one or more execution modes of the present invention, masking material comprises resist or photoresist, and the solution that is used for removal resist or photoresist comprises ammonium ceric nitrate and at least a other oxidant.

Other execution mode of the present invention provides and has for example basically removed the resist that experiences implanted ions and formed thus hard or the shell that is difficult to dissolve on resist fully.The other execution mode of the present invention provides single wet method (wet-only method) of for example peeling off the resist of accepting the high dose ion implantation (for example high dose ion is implanted and peeled off or HDIS), and wherein single wet method does not need to use any step relevant to plasma or step any and that vacuum is relevant.

According to following detailed description to exemplary embodiment of the invention, these and other feature of the present invention, theme and advantage will become apparent, and should understand by reference to the accompanying drawings the description of described execution mode.

Description of drawings

Fig. 1 has shown according to exemplary embodiment of the invention, removes the method for masking material from substrate.

Fig. 2 shown according to exemplary embodiment of the invention, x X-ray photoelectron spectroscopy X (XPS) analysis result of the wafer of having processed with masking material removal method.

Fig. 3 is according to exemplary embodiment of the invention, scanning electron microscopy (SEM) image of the cross section of silicon-on-insulator (SOI) wafer of having processed with masking material removal method.

Fig. 4 shown according to exemplary embodiment of the invention, the XPS analysis result of the silicon-on-insulator wafer of having processed with masking material removal method.

Fig. 5 shown according to exemplary embodiment of the invention, the viewgraph of cross-section of the integrated circuit of the encapsulation of having processed with masking material removal method.

Fig. 6 has shown to use has manganese or without the diverse location that contains cerium solvent clean test wafer of manganese.

Fig. 7 has shown the diverse location that uses rare CAN solvent clean test wafer.

Fig. 8 has shown use NH ₃With the ratio of TFA be the degree of the solution removal masking material of 1.002:1.

Fig. 9 has shown use NH ₃With the ratio of TFA be the degree of the solution removal masking material of 3.826:1.

Embodiment

Principle of the present invention will be described under the situation of explanation for the method for removal resist in this article.Yet, should be appreciated that, principle of the present invention is not limited to concrete grammar and the device of the exemplary demonstration of this paper and description.On the contrary, the purpose of the principle of the invention relates to widely for the technology of removing masking material.For this reason, can make many modifications within the scope of the present invention to shown execution mode.That is, with regard to embodiment described herein, not meaning that or should not being inferred as is restriction.

Implanted ions is can be with the implanted ions of dopant material to target material, the process in solid normally.The physical property before implantation is different from target material usually for the physical property of the material of implanted ions.Implanted ions is used in the making of semiconductor device, for example is used in the making of integrated circuit and silicon semiconductor device.Because the ion of implanting is the element that is different from target material, described ion can cause or cause chemical change in target material, and/or because target material can or even damage and the structural change that causes by implanted ions modification, infringement.Only as an example, typically comprise boron, boron difluoride, arsenic, indium, gallium, germanium, bismuth, xenon, phosphorus and antimony for the element of implanting species in semiconductor fabrication.Boron is the p-type alloy in silicon, because it contributes or cause " hole " (being the electron vacancy) in silicon.Arsenic is the N-shaped alloy in silicon, because it contributes or cause extra electronics in silicon.Implant in intrinsic silicon alloy for example boron and arsenic can to cause intrinsic silicon to become conductive, become semiconductor.One or more dopant materials can be implanted in target material.

Implanted ions is usually with dosage and energy characterization.Dosage is the implanted number of ions of the target material of unit are.Energy is just at the energy of implanted ion.Compare with older technology, more advanced semiconductor processes or manufacturing technology are typically used higher dosage and/or higher energy.In high dose ion was implanted (HDII), ion dose can be greater than about 5x10 ¹⁴Ion/cm ²And/or the average energy of ion can be for approximately 5000 electron-volts (KeV) to greater than 100KeV before ion affects target material or substrate.

The resist that comprises photoresist (being more typically masking material) is for form the radiation-sensitive materials of patterning coating on the surface of surface, for example substrate or target material.Resist is used in the making of semiconductor device, for example integrated circuit and silicon semiconductor device.A kind of purposes of resist in making semiconductor device is as the mask in the Semiconductor substrate with alloy selectivity implanted ions.Resist layer is put on the surface of Semiconductor substrate, or put on substrate or inner layer, the surface of the insulating barrier on semiconductor layer for example.A part of resist is exposed to radiation, the semiconductor regions (positive corrosion-resisting agent) that this part resist is equivalent to want implanted or not implanted semiconductor regions (negative resist).Then resist is exposed to developer, described developer assists in removing a part of resist, makes the resist that only stays required part.Positive corrosion-resisting agent is that the resist that wherein is exposed to radiation partly becomes and dissolves in the resist development agent and by a class resist of its removal.The unexposed resist part still is insoluble to the resist development agent and can not be removed by it.Negative resist is that the resist that wherein is exposed to radiation partly becomes and is insoluble to resist development agent and can not be by a class resist of its removal.Unexposed resist part in radiation still dissolves in the resist development agent and by its removal.Soluble resist part is dissolved by the resist development agent.With resist by being exposed to radiation patterning and develop by developer after, implanted ions occurs.Remaining resist stops that partly the ion of implantation arrives semiconductor or other material under resist.The ion that is stopped by resist is implanted in resist, rather than in following substrate.The semiconductor portions that is not covered by resist is by implanted ions.

Relatively wide scope has been contained in the radiation of various resist sensitivities.Only as an example, radiation can be ultraviolet light (for example approximately 300 to 400nm(nanometers)), deep UV (ultraviolet light) (DUV; For example approximately 10 to 300nm), in G, the H of mercury vapor lamp and I line (being respectively approximately 436nm, 404.7nm and 365.4nm) and x ray (for example approximately 0.01 to 10nm) scope.Radiation can comprise electron beam (e bundle) radiation in addition.Comprise the DUV light of about 193nm wavelength and comprise approximately that the light of 248nm wavelength is often used in radiation.Comprise approximately 193 and the photoetching technique of 248nm radiation be called as respectively 193nm photoetching and 248nm photoetching.

Due to the relatively high dosage of the implanting ions that is stopped by resist and/or high energy, resist is subject to ion at resist to be affected and absorbs and form shell or duricrust on the outside of ion or the outside.The anticorrosive additive material that has absorbed ion is hardened by ion.The ion that is absorbed by resist is stopped by resist and can not be implanted to semiconductor or the ion in other material under resist.The resist sclerosis can result from or be known as carbonization, polymerization or crosslinked polymer.Specifically, the ion that is penetrated in the resist perimeter can cause the perimeter (for example top of resist and side) of resist to become shell, and causes near the chemical bond in the interior zone of the resist of perimeter and become crosslinked.Known is (for example shell is insoluble in the solvent that some become known for peeling off) that is difficult to remove at resist stripping process mesochite.Because ion only penetrates into one section limited distance of anticorrosive additive material, so the shell major part is formed on the outside of resist.Because the implanted material in the bottom of resist or substrate cover, so shell can be formed on the top and side surface of resist, but is not formed on the bottom of resist or in inside.For typical resist, the shell at top is thicker than the shell of side, because ion is mainly implanted with downward incident direction usually.The thickness of resist shell depends on dosage and the implanted ions energy of implanting ions.The inside of shell or below anticorrosive additive material, the resist part that namely usually not affected by ion is called as main body resist or main body anticorrosive additive material.For example, the sclerosis of resist or crust make the outside of resist become insoluble or not soluble in water or some other aqueous solution (but not necessarily other all aqueous solution or all organic solvents).

Anticorrosive additive material often be directed to their plan the light wavelength of exposure or radiation type and customize.For this anticorrosive additive material, but reference exposure wavelength or emission types are called anticorrosive additive material.For example, anticorrosive additive material can be known as G line, I line, DUV(and comprises 193nm and 248nm name), x ray and e bundle.

High dose ion is implanted and to be peeled off (HDIS) is the process of peeling off the resist after the exposure of accepting HDII.Some HDIS processes can comprise dry run, for example plasma process and vacuum process.

The feature of HDIS process can comprise, for example amount of detachment rate, residue and exposure layer and the following for example loss of substrate, silicon substrate or the layer on silicon of layer.Sometimes finding residue after HDIS on substrate surface.Residue can result from the outer field incomplete removal of sputter, resist during HDII for example, and/or the oxidation of implanting ions in resist.Best, after the cleaning of peeling off and choosing wantonly, essentially no residue is answered on the surface, to guarantee high finished product rate and to eliminate the needs that other removing residues is processed.The example that another removing residues is processed is excessively to peel off, and for example continues stripping process after the point of removing the specified needs of photoresist.Excessively peel off the functional device structure of sometimes having removed below some, this can adversely affect performance of devices and rate of finished products, particularly for about 32 nanometers or lower than approximately super shallow-junction devices manufacturing technology and the metal gate transistor manufacturing technology of 32 nanometers.

Solution is the homogeneous mixture that is made of two or more materials.In this mixture, one or more solutes can be dissolved in solvent.Solution can comprise the liquid that for example is dissolved in other liquid.The ability that a kind of compound is dissolved in another kind of compound is called solubility.When adding other compound, the physical property of compound can change.

When using in this article, the implication of metal gate or metal gate electrode comprises metallic transistor (for example FET) gate electrode.Described metal can with other combination of materials.Metal in metal gate includes but not limited to Ti, Ta, W, Mo, Ru, Al, La, titanium nitride, tantalum nitride, ramet, titanium carbide, molybdenum nitride, tungsten nitride, ruthenium-oxide (IV), tantalum silicon nitride, titanium silicon nitride, carbon tantalum nitride, titanium carbonitride, titanium aluminide, calorize tantalum, TiAlN, tantalum nitride aluminium, lanthana or its combination.An instantiation of metal gate comprises titanium nitride (TiN).Notice that TinN has other purposes in electronic device, for example as the barrier metals between silicon and hard contact, and as electric conductor.It will be appreciated that the compound that is disclosed as metal gate material can have different stoichiometries.Therefore, titanium nitride will be represented as TiN in this article _x, tantalum nitride will be represented as TaN in this article _x, etc.

Ashing is the exemplary stripping process to the resist that does not experience HDII.Ashing comprises resist is heated to sufficiently high temperature, is usually removing by volatilization simultaneously with oxidation plasma is interactional to cause resist.Be used as the implanted ions mask for peeling off, especially for the anticorrosive additive material of the implanted ions mask of HDII, ashing is a kind of debatable method, because the resist shell that produces has resistance to podzolic process.Along with temperature raises, below shell or the pressure of inner volatility main body resist increase, cause the main body resist to break through or " explosion " goes out the shell of resist.This explosion causes the fragment of resist shell to be dispersed on the surface of wafer, and strong adhesion is in crystal column surface.May be difficulty or impossible with the fragment of resist shell from the crystal column surface removal, cause the rate of finished products degradation of the device that is for example just forming in wafer substrate.Importantly, the removal of carrying out the resist shell at the temperature that is enough to prevent explosion should be low to moderate.In general, use low the temperature that is enough to prevent explosion can extend resist and remove the needed time, thereby reduced the output (being the wafer of time per unit processing) of wafer.When thinner side shell was removed before thicker top shell, the problem of " lateral erosion of main body resist " can appear being called as, and cause the main body resist to be removed the below of shell in the above, be not completely removed simultaneously.The lateral erosion of main body resist can cause the fragment fracture of top shell come and with substrate contact, strong adhesion in substrate and the rate of finished products that for example is reduced in the device that forms in substrate.In addition, need to remove resist fully fully or basically from wafer, comprise the shell of resist, just make in substrate (for example semiconductor or Silicon Wafer) or the upper device that forms has acceptable rate of finished products.

As above summarize, three importances that resist is peeled off are: (i) peel off at relatively low temperature (for example low be enough to prevent explosion); (ii) relatively short resist splitting time is to provide acceptable wafer throughput; (iii) resist is removed basically fully from substrate surface.The 4th importance that resist is peeled off relate to can by resist peel off cause to the infringement of substrate or undesirably removed a part of substrate.This infringement is undesirable, for example because this can cause in substrate or on the structure that forms and device (for example in semiconductor crystal wafer or Silicon Wafer or on the transistor or other electronic device that form) do not have function or function not good.Substrate is defined as comprising silicon, metal gate or its combination in this article, wherein in manufacture process afterwards with material layer depositions on described substrate." silicon " can be defined as comprising Si, polycrystalline Si, single crystalline Si and SiGe and other material for example silica, thermal oxide, SiOH and SiCOH.Silicon is comprised in silicon-on-insulator (SOI) wafer, and described silicon-on-insulator (SOI) wafer for example can be used as being used for electronic device for example substrate or the part substrate of FET and integrated circuit.The wafer of other type also can comprise silicon.To the example of the infringement of backing material or removal include but not limited to silicon or titanium nitride (TiN), for example be comprised in the TiN in the metal gate of FET or be comprised in semiconductor and metal between barrier in infringement or the removal of TiN.Described infringement for example can comprise dissolving (corrosion), be transformed into different solid-phases for example oxide or both combinations.

As will describe in this article, the purpose of embodiments of the present invention is effectively to remove the resist after implanted ions, and described resist for example can be used as the mask that stops in silicon, other semiconductor technology and microelectron-mechanical (MEM) technology.Known method that be used for to remove resist comprises the combination of dry method corrosion (for example plasma corrosion, vacuum process) and wet method corrosion (for example chemolysis), perhaps uses based on for example wet method corrosion of the mixture of sulfuric acid and hydrogen peroxide (SPM) of the chemistry of sulfuric acid.The common shortcoming of the many known resist stripping means that uses at present is included in the photoresist of the crust that exists on crystal column surface after implanted ions and removes not exclusively.Along with the progress of semiconductor technology, advanced technology node the have relatively high expectations implanted ions of dosage and higher energy level, this has increased the crust that implanted ions stops resist.In addition, shown that losing agent or SPM by dry method soaks and remove resist and produced the loss of too much silicon and alloy and made may damaging of silicon structure tender.

Method of the present invention can be used for peeling off implanted with HDII, for example use approximately 5x10 ¹⁴Above ion/cm ²And/or the resist of implanting to surpass the about energy of 5KeV.Yet method of the present invention is not subjected to such restriction, and can be used for peeling off and use less than 5x10 ¹⁴Ion/cm ²With the resist to implant lower than the energy of 5KeV.Method of the present invention can be used for peeling off by comprising the resist of the program generation patterning that is exposed to one of following emission types: e bundle, the x ray, and wavelength is equivalent to G line, H line, I line DUV, approximately 248nm and the about light of 193nm.

As describing in this article, embodiments of the present invention comprise the method for HDIS, described method for example comprises lower than approximately 90 degrees centigrade (C) (for example approximately 35 to 90C, and/or low be enough to prevent explosion) temperature, be used for carrying out HDIS less than the reasonable time of approximately 80 minutes (for example approximately 5 to 75 minutes), basically remove fully resist (for example approximately 99% removing) and to the infringement of backing material remove minimum or do not have (for example the removal of TiN is less than about 50 dusts, the silicon loss not or minimize and the SOI wafer in the limited oxidation of component).The HDIS of the inventive method can cause seldom or there is no remaining resist or a resist shell residue, for example in solution or be deposited on wafer.

As describing in this article, embodiments of the present invention are used the resist reaction of oxidation chemistry and implanted ions, thereby make resist dissolve in common solvent (for example water).Oxidation chemistry can comprise for example oxygenated functional group or chemical bond.Specifically, make the crust part of resist or to contain the part of polymer complete or basically solvable.

As describing in this article, embodiments of the present invention also provide the stable aqueous solution of the salt that contains the lanthanide series cerium or comprise cerium, and described solution can be peeled off the resist of high density implanted ions.

As describing in this article, embodiments of the present invention can be used for many technology, include but not limited to be commonly called the production of integrated circuits technology of the 32 following technology of nanometer.

As describing in this article, embodiments of the present invention can be used for for example forming electronic device, FET for example, or enter by block dopant (for example alloy of implanted ions) source region, drain region and the channel region that other zone except source region, drain region or the channel region implanted forms FET.Embodiments of the present invention for example can be used for forming conductor by covering the zone that will become conductor and maybe will become other zone except conductor.

Fig. 1 has shown substantially according to exemplary embodiment of the invention, is used for removing from substrate the method 100 of masking material.Described method can be the HDIS method.Method 100 for example can comprise the wet chemistry that does not use plasma or vacuum process.Can think that method 100 is not relate to dry process single wet method of (namely relating to the processing of plasma or vacuum process), but one of ordinary skill in the art would recognize that, imagine the further dry process before or after wet treatment.

The step 110 of method 100 comprises provides substrate.Described substrate can be wafer, and semiconductor crystal wafer for example is on described substrate or the inner electronic device that forms.Described electronic device can comprise transistor, and for example FET, comprise the FET that comprises metal gate (metal gate that for example comprises TiN).When wafer was provided, some electronic devices can partly form, and for example can complete the implanted ions of source/drain region or channel region before wafer is provided.Only as another example, before the deposition of TiN layer can occur in wafer is provided.Masking material can adhere to the upper surface of wafer.Masking material can comprise anticorrosive additive material, for example photo anti-corrosion agent material.There is no the implanted ions of a part of wafer that masked material covers in implantation during, masking material can be by implanted ions (for example HDII).The implanted ions of masking material can cause the skin that forms sclerosis, crust, polymerization and/or charing in masking material.The skin of masking material may be difficult for molten, for example is not soluble in cleaning agent, for example the following cleaning agent of describing in step 130 and table 1.

The step 120 of method 100 comprises substrate, comprises that the masking material of adhesion contacts with solution.Described solution comprises the lanthanide series cerium.Although cerium is disclosed as the active element that adopts in described solution, should be understood that and to use the element that has with the same or analogous chemical characteristic of cerium.For example, other lanthanide series can have some and the similar characteristic of cerium.Know that generally lanthanide series is those element with atomic number of 57 to 71, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetiums.

But at least a salt or the co-ordination complex of described solution containing element cerium.Cerium salt can be for example ammonium ceric nitrate.The chemical formula of ammonium ceric nitrate can be expressed as Ce (NH ₄) ₂(NO ₃) ₆Or (NH ₄) ₂Ce (NO ₃) ₆Ammonium ceric nitrate is also referred to as CAN, cerium ammonium nitrate (V) and ammonium ceric nitrate.When using in this article, CAN refers to ammonium ceric nitrate.CAN is the orange water soluble salt that can be used as oxidant.Operable other cerium salt includes but not limited to cerous nitrate, Cericammoniumsulfate, cerous sulfate, cerous hydrosulfate, perchloric acid cerium, methanesulfonic acid cerium, trifluoromethanesulfonic acid cerium, cerium chloride, cerium hydroxide, carboxylic acid cerium, beta-diketon cerium, trifluoroacetic acid cerium and cerous acetate.In some embodiments of the present invention, described solution can comprise more than a kind of above-mentioned cerium salt.Preferably, cerium salt comprises ammonium ceric nitrate.Based on the total weight of solution, the valid density scope of cerium salt be approximately 0.01 % by weight to about 70 % by weight, preferred approximately 0.01 % by weight to about 30 % by weight.

Be tending towards being hydrolyzed along with passage of time and generate precipitation owing to containing the cerium aqueous solution, particularly when remaining on over room temperature when (namely surpassing approximately 20 to 25 ℃), therefore can adopt to add acid or other compound as stabilizer, in order to stablize described solution.The concentrated solution of cerium salt in water is normally stable, but at the approximately temperature of 70 ℃ that raises, and cerium salt causes that due to hydrolysis and/or redox reaction precipitation generates.Yet in strongly acidic solution, this precipitation is soluble.For this reason, CAN can be formulated in acidity or other stable, so that stabilizing solution and prevent or limit the precipitation of cerium.The effect of stabilizer is to reduce precipitation, for example by the sediment (for example precipitation of one or more components of CAN or CAN or sediment) of dissolving from solution.For example, the 20%CAN aqueous solution approximately under 70 ℃, after the one relatively short period of approximately 30-45 minute, can generate a large amount of precipitations and become fully opaque.Under same CAN concentration and temperature, when solvent comprises approximately 5.5% nitric acid and approximately during 74.5% water, even after 24 hours also almost without precipitation.

The stabilizer of considering comprises but is not limited to ammonium salt, strong acid, weak base salt and any combination thereof.Can use one or more stabilizers.For example, the ammonium compounds in CAN, described solution also can comprise for example ammonium salt.Add ammonium salt also can help stabilizing solution.Ammonium salt includes but not limited to ammonium chloride, ammonium nitrate, ammonium hydroxide (being ammonia), ammonium sulfate (NH ₄) ₂SO ₄, ammonium hydrogen sulfate, ammonium acetate, ammonium perchlorate (NH ₄ClO ₄), at least a in trifluoroacetic acid ammonium (ATFA), methanesulfonic acid ammonium, carboxylic acid ammonium, beta-diketon ammonium and trifluoromethanesulfacid acid ammonium.For example, comprise about 20%CAN and approximately the aqueous solution of 12% ammonium nitrate approximately remained clarification in 2.5 hours at 70 ℃, by contrast, be less than 1 hour for independent CAN.The effect of ammonium chloride (for example with 5% concentration use) is similar, but due to chlorine and Ce (4+) sluggish and to the negative effect of storage period existence.In one embodiment, stabilizer comprises the trifluoroacetic acid ammonium.For example, the 20%CAN solution that contains 4% trifluoroacetic acid ammonium approximately remained transparent in 14 hours at 70 ℃.Other compound as the stabilizer of the preparation of CAN and water (for example DI water) includes but not limited to weak base salt and strong acid.The acid of considering includes but not limited to one or more in nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, glacial acetic acid, periodic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid and poly-sulfonic acid (for example poly-(4-styrene sulfonic acid)).Additionally, perhaps additionally, other water-soluble polymer be can add, polyacrylic acid, polymethylacrylic acid and polymeric acid included but not limited to.The example of polymeric acid includes but not limited to poly, polytetrafluoro sulfonic acid, polyethylene maleic acid and polystyrene carboxylic acid.The valid density scope of these stabilizers is that approximately 0.01 % by weight is to about 60 % by weight based on the total weight of solution, and preferred approximately 0.5 % by weight is to about 25 % by weight.Should be appreciated that, any combination of aforementioned stable agent is taken into account: only ammonium salt, only strong acid, only any combination of weak base salt or ammonium salt, strong acid and weak base salt.When solution comprised CAN and perchloric acid, solution preferably was not used in corrosion chromium film.

Advantageously, can be by coming original position to generate the trifluoroacetic acid ammonium ammonia and trifluoroacetic acid (TFA) combination.Can change ammonia with respect to the mol ratio of TFA, to increase the stable of solution.For example, work as NH ₃During greater than 1:1, it is more stable that solution is tending towards with the mol ratio of TFA.Preferably, NH ₃With the mol ratio of TFA in greater than the about 0.8:1 scope to approximately 5:1, preferred approximately 2:1 to about 3:1.Simultaneously, the mol ratio of preferred ammonia and TFA greater than about 1:1 to approximately 2:1, preferred approximately 1.2:1 extremely approximately in the scope of 1.7:1.It will be appreciated that these ratios are exemplary, and can change with effective removal masking material with the need, this is that the technical staff easily determines.

Described solution also can comprise other solute or solvent.For example, described solution also can comprise water (H ₂O), for example deionized water (DI water) is as solvent.Execution mode comprise based on the approximately 1wt% of total solution weight to about 40wt% cerium salt and approximately 60wt% to about 99wt%DI water, preferred approximately 5wt% to about 35wt% cerium salt and approximately 65wt% to about 95wt%DI water, be more preferably approximately 10wt% to about 30wt% cerium salt and approximately 70wt% to about 90wt%DI water, and most preferably from about 15wt% to about 25wt% cerium salt and approximately 75wt% to about 85wt%DI water.The exemplary formulation of described solution comprises approximately 20 % by weight CAN and approximately 80 % by weight DI water.Considered other preparations, for example comprised the preparation of CAN and acidic aqueous solution, described acidic aqueous solution comprises anti-oxidant acid for example acetic acid, methanesulfonic acid, trifluoroacetic acid and other fluorocarboxylic acid.Anti-oxidant solvent for example sulfolane and nitromethane also is considered as the part of preparation.

Except ammonium salt, other solute and solvent and stabilizer, contain cerium solution and also can comprise at least a other oxidant.Other oxidant of considering comprises and contains at least a in ruthenium (Ru), iridium (Ir), manganese (Mn) and osmium (Os) compound.For example, oxidant comprises but is not limited to RuO ₄, OsO ₄, KMnO ₄, NH ₄MnO ₄, RuCl ₃, OsCl ₃, Ru (NO ₃) ₃, Os (NO ₃) ₃, Mn (NO ₃) ₂XH ₂O, MnCO ₃, MnSO ₄XH ₂O, Mn (C ₂H ₃O ₂) ₂XH ₂O, MnCl ₂, MnBr ₂, and the combination.Advantageously, when having Ce (IV), can generate in position described other oxidant species.For example, RuO ₄Be expensive and poisonous, still, because it can regenerate in position, therefore can use the RuO of low concentration under Ce (IV) exists ₄And Ce (IV).In addition, can use Ru, Ir or Os salt, for example RuCl of low price ₃, because it will be by generating in position oxidised form, for example RuO with Ce (IV) reaction ₄Similarly, exist under the condition of cerium under low pH, Mn (II) salt is oxidized to Mn (VII) salt, i.e. permanganate (MnO ₄ ^-), described permanganate can strengthen for example oxidation activity of cerium of other oxidant of existing in composition.For example, described other oxidant can be Mn (NO ₃) ₂XH ₂O, MnCO ₃, MnSO ₄XH ₂O or its combination, wherein Mn (II) ion is oxidized to Mn (VII) under Ce (IV) exists.To comprise other oxidant advantage that for example Mn (II) salt is relevant and comprise and have two kinds of oxidants and regenerate the permanganate that reacted under Ce (IV) exists.In preferred embodiment, described other oxidant comprises Mn (NO ₃) ₂XH ₂O, MnCO ₃, MnSO ₄XH ₂O or its combination.In particularly preferred embodiments, described other oxidant comprises Mn (NO ₃) ₂XH ₂O。Can generate in position strong oxidizer and facilitate other element of peeling off to include but not limited to that chromium is (as Cr ³⁺Salt adds, Cr ³⁺Salt is oxidized to chromate or bichromate in position), vanadium is (as VO ²⁺Salt adds, VO ²⁺Salt is oxidized to V in position ⁵⁺), bromine (as bromide for example ammonium bromide or manganous bromide add, described bromide is oxidized to bromate BrO ₃ ^-) and iodine (for example can be used as ammonium iodate adds, ammonium iodate is oxidized to periodate).Also can directly add high oxidation state in initial soln, for example for the ammonium dichromate for Cr, for the bromic acid ammonium for Br, for the periodic acid for I and the ammonium persulfate for active oxygen.One skilled in the art will recognize that, depend on solubility of additive and be easy to dissolubility and other process Consideration, above-claimed cpd can be added as pure solid or the aqueous solution.

In addition, solution of the present invention also can comprise at least a surfactant that is selected from anion, nonionic, cation and zwitterionic surfactant, preferred at least a non-ionic surface active agent.For example and preferably, suitable non-ionic surface active agent can comprise fluorine-containing surfactant, ethoxylation fluorine-containing surfactant, polyox-yethylene-polyoxypropylene block copolymer, alkylphenol ethoxylate, castor oil ethoxylate, fatty acid ethoxylate, alkyl ethoxylate, alkyl phenyl ethoxylate, polyoxyethyleneglycododecyl dodecyl ether, fluorochemical polyether and comprise above-mentioned at least a combination.For example, non-ionic surface active agent can be the ethoxylation fluorine-containing surfactant for example

FSO-100 or FSN-100 fluorine-containing surfactant (DuPont Canada Inc., Mississauga, Ontario, Canada), polyox-yethylene-polyoxypropylene block copolymer for example

17R4 or 25R4(BASF), polyoxyethyleneglycododecyl dodecyl ether is for example

35P, alkylphenol ethoxylate are for example

X-100, castor oil ethoxylate for example CO(Huntsmen Chemical, Texas, USA), fatty acid ethoxylate is for example E-400MO(Huntsmen Chemical, Texas, USA),

604(Air Products), fluorochemical polyether is POLYFOX for example ^TMPF-159(Omnova Solutions, Inc.), and combination.Preferably, non-ionic surface active agent can be

FSO-100, FSN-100,

17R4,

25R4,

35P,

CO-42,

E-400MO, POLYFOX ^TMPF-159 and combination thereof.Also can use anionic fluorosurfactants, for example fluorine-containing surfactant for example

UR and

FS-62(DuPont Canada Inc., Mississauga, Ontario, Canada), fluorine-containing alkyl sulfonic acid ammonium NOVEC for example ^TM4300(3M), perfluoro alkyl sulfonic acid CAPSTONE for example ^TMFS-10(DuPont), sodium alkyl sulfate for example ethylhexyl sulfate ( 08), alkylsurfuric acid ammonium, alkyl (C ₁₀-C ₁₈) ammonium carboxylate salt, sodium sulfosuccinate and ester thereof for example sodium sulfosuccinate dioctyl ester, alkyl (C ₁₀-C ₁₈) sulfonate sodium, two anionic sulphonate surfactant D owFax(The Dow Chemical Company, Midland, Mich., USA) and combination.In addition, considered the mixture of nonionic and anion surfactant here.

The execution mode of solution of the present invention includes but not limited to the solution that (i) comprises cerium salt and solvent, formed or basically be comprised of them by them; (ii) solution that comprise cerium salt, solvent and ammonium salt, forms or basically formed by them by them; (i) solution that comprise cerium salt, solvent and acid, forms or basically formed by them by them; (iv) solution that comprise cerium salt, solvent, ammonium salt and acid, forms or basically formed by them by them; (v) solution that comprise cerium salt, solvent, acid and other oxidant, forms or basically formed by them by them; (vi) solution that comprise cerium salt, solvent, acid and manganese (II) salt, forms or basically formed by them by them; (vii) solution that comprise cerium salt, solvent, ATFA and other oxidant, forms or basically formed by them by them; (viii) solution that comprise cerium salt, solvent orange 2 A TFA and manganese (II) salt, forms or basically formed by them by them; (ix) solution that (vii) comprise cerium salt, solvent, nitric acid and other oxidant, forms or basically formed by them by them; (viii) solution that comprise cerium salt, solvent, nitric acid and manganese (II) salt, forms or basically formed by them by them.

Effectively pharmaceutical solutions includes but not limited to comprise approximately 2% to the about solution of 70%CAN and solvent.Effectively examples of solvents includes but not limited to comprise approximately 1% to about 55% dense perchloric acid, approximately 5% to about 60% acetic acid, approximately 1% to about 50% nitric acid (HNO ₃), approximately 1% to about 50% sulfuric acid, approximately 1% to about 50% methanesulfonic acid (CH ₃SO ₃H), approximately 1% to about 55% trifluoromethanesulfonic acid (CF ₃SO ₃H) and/or approximately 1% to the about solvent compositions of 55% poly-sulfonic acid (for example polystyrolsulfon acid).Consider that described solution can comprise only a kind of or more than a kind of acid.Only as an example, substrate can be immersed in approximately 10 to the aqueous solution of about 75% poly-sulfonic acid.The poly-sulfonic acid concentrations of using can be approximately 10 to about 50% dense poly-sulfonic acid in water.Poly-sulfonic acid can be for example polystyrolsulfon acid.

In preferred embodiment, pharmaceutical solutions is diluted to total weight based on solution, CAN concentration is less than about 10 % by weight, preferred approximately 0.5 % by weight to about 8 % by weight, be more preferably approximately 1% to about 6% scope.Should " weak solution " can there is no stabilizer, perhaps comprise stabilizer.For example, this weak solution can comprise CAN and water, is comprised of them, or basically is comprised of them.Perhaps, this weak solution can comprise CAN, at least a stabilizer, He Shui, is comprised of them, or basically is comprised of them.Advantageously, can prepare weak solution by the CAN solution of dilution higher concentration.Perhaps, solid CAN can be joined water, for example as required in warm water or boiling water to realize that CAN is dissolved in wherein, prepare weak solution.It will be appreciated that when using term " solution " in method is described, it is corresponding to any solution of describing herein, rare or other.

By substrate is immersed in solution, substrate can contact with solution.Also imagined other contact method, for example with solution spray, cleaning or washing substrate, and substrate has been stirred in solution.Substrate typically contacts the specific time period with solution.Approximately 5 and approximately the time period between 60 minutes be contact with solution for substrate effective time section example.

Also can carry out the process of peeling off resist in spray in batch instrument or single-wafer device, wherein the latter will have several advantages, include but not limited to be chosen in use low-flash solvent under blanket of nitrogen for pre-treatment and/or the post-processing step chosen wantonly, more volatile antioxidant composition and cerium-containing compound can be made up, and the temperature of cerium-containing compound treatment step can be raised near 100 ℃ to shorten this process.

In another embodiment, can be designed for the process of polycrystalline circle spraying instrument, the weak solution that will describe thus (for example 1-2 liter/min of clock) on large quantities of wafers (for example Zeta instrument of FSI) of spraying economically herein.Advantageously, this will reduce the have cost relevant to the masking material removal.In another execution mode of described process, can use the totally-enclosed chamber that to take the appropriateness pressurization herein.Can develop and to operate and with faster similar procedure, further to save solution and process time under higher temperature (for example 130-150 ℃).

Solution and/or substrate can be heated to and/or maintain specific temperature or in specific temperature range.Low as to be enough to prevent that the temperature of masking material explosion from being preferred.Other Consideration for example boiling point of water also may determine the upper limit of temperature range.Example for the effective temperature of the solution of execution in step 120 in the about temperature between 35 and 90 ℃.

Described solution can be removed at least a portion masking material, if not the words of basically all removing.In the situation that best, described solution can be removed all (100%) masking materials.Substrate is contacted one or more characteristics that can change masking material with solution with the masking material that adheres to.Substrate is contacted outside or the shell that can make masking material, particularly masking material with solution with the masking material that adheres to solvable, perhaps than more solvable before contacting with solution.For example, masking material is dissolved in or more dissolve in step 130 and the table 1(see below) liquid or cleaning agent.Therefore, the cleaning agent of describing in step 130 can be by removing the masking material dissolving material of sheltering of all or some remainder.Cleaning agent can add or separately machinery remove (for example rinse, clean or wash off) masking material.

The step 130 of method 100 is that substrate is contacted with cleaning agent with any remaining masking material that adheres to substrate.In an embodiment of the invention, after step 130 occurs in step 120.Cleaning agent has been removed the forward masking material of some or all from substrate surface.In preferred embodiment, cleaning agent has been removed whole remaining masking materials basically, perhaps enough at least remaining masking materials with just provide in substrate or on the reasonable or needed rate of finished products of the electronic device that forms.Described remaining masking material can comprise all or part of outer and/or all or part of material of main part.Can make in advance all or part of skin dissolve in cleaning agent by step 120.

By substrate is immersed in cleaning agent, substrate can contact with cleaning agent.Also imagined other contact method, for example sprayed with cleaning agent or wash substrate and substrate is stirred in cleaning agent.Substrate typically contacts the specific time period with cleaning agent.The exemplary time period will be presented in the experimental description of back to method.

Cleaning agent and/or substrate can be heated to and/or maintain specific temperature or in specific temperature range.Approximately 55 and approximately the temperature between 90 ℃ be effective.

Cleaning agent can comprise for example sulfuric acid (H ₂SO ₄) or sulfuric acid and water (for example DI water).Cleaning can comprise that single cleans or a series of cleaning procedure.For example, cleaning can be included in the single cleaning in water, sulfuric acid or sulfuric acid and water.The example of a series of cleaning procedures is at first to clean in water, then cleans in sulfuric acid or sulfuric acid and water, then randomly cleans again in water.Other cleaning is also taken into account.Dry can occur between cleaning, after final cleaning and between contact solution and first cleaning.Drying can occur in and comprise nitrogen (N ₂) atmosphere in.

In a preferred method, the method for removal masking material comprises that prerinse (for example using the rare or concentrated sulfuric acid), the substrate of substrate contact with solution (or weak solution) and the rear cleaning (for example using the rare or concentrated sulfuric acid) of substrate.For any photoresist of final removal with contain the Ce particle, optionally carry out of short duration cleaning with rare SC1 solution.Between various chemical cleaning, use the washed with de-ionized water substrate.

In embodiments of the present invention, step 120 and 130 be enough to remove all, almost all or basically whole (for example approximately 100%) masking materials.Do not need to relate to the step of plasma, plasma corrosion or vacuum process, but can use when preferred, this is that those skilled in the art can easily determine.

The method of describing is herein effectively also removed masking material efficiently from substrate, wherein said masking material is contained in the layer that forms on first's substrate at least, and wherein said masking material has stopped first's dopant material contact at least described first at least substrate.Masking material is included in the resist of following at least a lower exposure: (i) be included in the approximately light of the one or more wavelength between 10 and approximately 400 nanometers; (ii) x x radiation x; (iii) electron beam irradiation.Preferably, the dopant material of first comprises the ion that is implanted in masking material, and wherein said ion comprises following at least a: boron, boron trifluoride, indium, gallium, germanium, bismuth, arsenic, phosphorus, xenon and antimony.Substrate also can comprise the dopant material of second portion, and the dopant material of described second portion comprises the ion that is implanted in the second portion substrate.In one embodiment, described method comprises by solution removal first's masking material at least, and masking material is contacted to remove the masking material of second portion with liquid.Preferably, described liquid comprises following at least a: water, acid and sulfuric acid (H ₂SO ₄).

In yet another embodiment of the present invention, except cleaning, wafer can be contacted to dissolve and/or remove with the solution of removal particle the sediment that contains Ce (IV) with instrument.The technical staff can be appreciated that, can before cleaning step, after cleaning step or before cleaning step and afterwards, the solution of removing particle be contacted with wafer.

Method 100 can be recognized as at least part of formation or make for example FET, integrated circuit or the MEM method of microelectromechanical systems (MEMS) for example of electronic device.Only as an example, can be by forming substrate (substrate that for example comprises titanium oxide), implanted ions (for example HDII) photoresist and with photoresist and the solution that comprises cerium (for example CAN) or comprise cerium and the solution of at least a other oxidant contacts, forming electronic device.

MEM or MEMS are the devices of making at the upper integrated mechanical organ (for example switch, transducer or driver) of common substrate (substrate that for example comprises silicon and/or TiN) and electronic device (for example transistor, inductor, resistance, electronic storage element, capacitor and electric conductor) by the micro production technology.For example, fall the part Silicon Wafer with selective corrosion or add the micromachined process of new construction layer to make micromechanical component.Usually use the process compatible with complementary metal oxide semiconductors (CMOS) (CMOS) IC technology to make MEM on silicon substrate.The making of MEM can comprise removal resist described according to embodiment of the present invention.

Method of the present invention 100 and other method for example can comprise water or solubility in acid cerium (IV) compound are reduced into and sometimes be water-insoluble cerium (III) compound.

Control the acidity of solution or pH and controlled cerium salt and described at least a other oxidant in the situation that there is solubility in mixture or solution.For example can come Controlled acidity or pH by the amount of the acid in the solution of aqueous peracid solution (namely comprising acid and the solution of water and cerium), for example following examples 2 and 3.Even there is not the acid that adds, low pH has also been guaranteed in the partial hydrolysis of Ce (IV).Typically, the pH of solution is less than 3, preferably less than 2, and most preferably less than 1, but be not less than 0, because very high acid concentration can cause for example excessive corrosion of TiN of some grid materials.

By following non-limiting example, principle of the present invention is described more fully.In an embodiment, percentage is by weight.

Embodiment A

Table 1 has illustrated four embodiment of implementation method 100.All embodiment are all for removing resist from the substrate that has adhered to resist (being masking material).Arsenic ion with prescribed dose and energy is implanted resist.The step 110 of method 100 comprises provides the above-mentioned substrate that has adhered to resist.

Table 1

All dosage that table 1 provides, energy, solution composition, solute composition, temperature and time are approximation.

Be important to note that principle of the present invention is not limited to any definite measured value or scope.Therefore, the measured value that provides herein and scope are intended to the Illustrative introduction and how form solution of the present invention and use described solution, and need to not make any excessive experiment by those of ordinary skills side.Therefore, measured value and scope those that provide except Illustrative in this article are considered within the scope of the invention.

In embodiment 1, the solution of method 100 comprises approximately 20%CAN and approximately 80%DI water.After solution being heated to approximately 70C, substrate is immersed in (i.e. contact) solution approximately 30 minutes.This immersion in solution is comprised in the step 120 of method 100.

Substrate is shifted out from solution, approximately cleaned in 30 seconds by soaking in DI water, and at nitrogenous (N ₂) atmosphere in dry.This cleaning is comprised in the step 130 of method 100.

In embodiment 2, the solution of method 100 comprises approximately 15%CAN and approximately 85% solvent.Solvent is included in DI water approximately 10% dense perchloric acid (HClO ₄) (i.e. approximately 10% dense perchloric acid and approximately 90% water).Dense perchloric acid comprises approximately 70% perchloric acid and for example about 30% water.After solution being heated to approximately 60C, substrate is immersed in solution approximately 30 minutes.This immersion in solution is comprised in the step 120 of method 100.

Substrate is shifted out from solution, and approximately stood the first cleaning procedure in 30 seconds by soaking in DI water.Then substrate is dry in nitrogenous atmosphere.Then substrate stands the second cleaning procedure, after described the second cleaning procedure is included in the temperature of sulfuric acid solution being adjusted to about 19C, soaks in the concentrated sulfuric acid (i.e. approximately 96.5% sulfuric acid and approximately 3.5%DI water) approximately 15 minutes.Then substrate stands the 3rd cleaning procedure, and described the 3rd cleaning procedure is included in of short duration cleaning in mobile DI water.Only as an example, flowing water can be room temperature or near room temperature, and the duration of the 3rd cleaning procedure can be approximately below 1 minute.Then substrate is dry in nitrogenous atmosphere.This cleaning comprises being comprised in first, second and the 3rd cleaning procedure in the step 130 of method 100.

In embodiment 3, the solution of method 100 comprises approximately 20%CAN and approximately 80% solvent.Solvent is included in approximately 50% the glacial acetic acid (CH in DI water ₃COOH) (i.e. approximately 50% glacial acetic acid and approximately 50%DI water).After solution being heated to approximately 70C, substrate is immersed in solution approximately 60 minutes.This immersion in solution is comprised in the step 120 of method 100.

In embodiment 4, the solution of method 100 comprises approximately 55%CAN and approximately 45%DI water.After solution being heated to approximately 80C, substrate is immersed in solution approximately 15 minutes.This immersion in solution is comprised in the step 120 of method 100.

Substrate is shifted out from solution, approximately cleaned in 30 seconds by soaking in DI water, and dry in nitrogenous atmosphere.This cleaning is comprised in the step 130 of method 100.

Carry out experiment to measure the CAN chemistry to the impact of TiN.Select TiN to be because TiN is comprised in some FET for example in the metal gate of part with the FET of illustrative method formation of the present invention.This experiment comprises that the TiN that will be deposited on wafer is exposed to the different time of the 20%CAN aqueous solution at two temperature, and measures from the titanium oxide (TiO of the formation of the titanium in the TiN layer in the past before wafer and TiN are exposed to CAN _x) layer thickness.Also measured the thickness (remaining thickness after namely soaking) of remaining TiN layer and remaining Si oxide skin(coating) in CAN.

Table 2

Wafer	Temperature (℃)	Time (minute)	TiO _x/ TiN/Si oxide (dust)
				Contrast	85	0	4/110/~2000
1	85	30	12/100/~2000
				2	85	60	35/80/~2000
3	65	10	12/95/~2000
				4	65	15	27/95/~2000
5	65	30	37/85/~2000

Above table 2 shown experimental result, the compatibility that the CAN that is used as HDIS and TiN are favourable has been described.Obtained experimental result by application process 100.In this case, step 110 comprises the Silicon Wafer that the TiN layer that applies have an appointment (～) 2000 dust silica (Si oxide) and the nominal on the Si oxide skin(coating) (approximately) 130 dusts is provided.The wafer of the such coating that provides is called as original wafer.All temperature, time and the size that provide in table 2 are approximation.

Step 120 comprises wafer is immersed in about 20%CAN and approximately reaches time specified in table and temperature in the solution of 80%DI water.Step 130 comprises wafer being soaked in solution afterwards cleans in DI water, and dry in comprising the atmosphere of nitrogen.After immersion in CAN, cleaning and drying, by the thickness of reflectometry rest layers.It is as shown in the table, and rest layers comprises top TiO _xLayer, TiN layer and Si oxide skin(coating), described TiN layer are the remainders of the original TiN layer before immersion in CAN, and described Si oxide skin(coating) is the original Si oxide skin(coating) before immersion in CAN basically.The contrast wafer is not soaked in CAN.For the contrast wafer, recorded the approximately thick TiO of 4 dusts _xLayer, and recorded the TiN layer that approximately 110 dusts are thick.The measured thick TiO of approximately 4 dusts _xLayer and measured TiN layer thickness be from approximately 130 obviously being down to approximately 110 dusts (namely approximately 20 dust thickness differences) not because CAN causes, but other reason is arranged, and is not for example oxidation or the experimental error of the TiN that causes due to CAN.Reason whatsoever, in calculating the impact of CAN on TiN, the TiO that produces from be immersed in CAN _xDeduct the measured approximately TiO of 4 dusts of contrast wafer in the measured thickness of layer _xLayer thickness is rational.Equally, it is rational deducting the TiN layer thickness of about 20 dusts poor among CAN from the TiN layer difference of the wafer that soaks and original wafer.

For example, this table shown for wafer 2, and when approximately soaking approximately 60 minutes under 85 ℃ in CAN, the TiN layer is reduced to approximately 80 dusts from the about contrast wafer thickness of 110 dusts, and has formed the TiOx layer that approximately 35 dusts are thick, namely than thick approximately 31 dusts of contrast wafer.As shown in Table TiN layer and TiO _xIt is acceptable that the thickness of layer is peeled off with element manufacturing for HDIS.Be important to note that, if TiN sample that will be identical with sample used herein is immersed in common wet method resist stripping mixture (hot solution that namely contains sulfuric acid and hydrogen peroxide), whole TiN layer will be dissoluted in less than 1 minute.This is not obviously the situation of preparation disclosed in this invention.

Fig. 2 has shown the contrast wafer of table 2 and x X-ray photoelectron spectroscopy X (XPS) analysis result of wafer 5.Trace 210 representative contrasts, the wafer before namely soaking in CAN solution.Wafer 5 after trace 220 representatives are soaked.Being positioned at approximately, 458 and 449 electron-volts (EV) in conjunction with the titanium of the peak in the middle of energy corresponding to oxidation, is most possibly the form of titanium oxide.Be positioned at approximately 456 and 457 electron-volts in conjunction with can in the middle of the peak that occurs as acromion corresponding to titanium nitride.Can qualitative estimation TiO from the XPS data _xThickness is not less than approximately 20 to 30 dusts.From this result of XPS analysis with reflectometry and experimental result that be provided in table 2 is very consistent.Be important to note that also can detect in trace 220 be positioned at 456 with 457EV in the middle of acromion, show by method 100 and carry out reprocessing, TiN still be present in the TiOx top layer below.

Below table 3 shown with comprising a part on Silicon Wafer, silicon-on-insulator (SOI) wafer of the solution-treated of CAN, scribbling the part of wafer of the responsive resist of 193nm and the impact of these samples of TiN.All temperature and times that provide in table 3 are all approximations.

By processing sample at about 20%CAN and time of approximately soaking appointment in the solution of 80%DI water at the temperature of appointment.For Silicon Wafer sample and 193 resist samples, after soaking in CAN solution, in room temperature (RT) or near sulfuric acid cleaned under room temperature approximately 5 minutes.The analysis of sample is by XPS after immersion and cleaning (if any), and for the Silicon Wafer sample, also by total reflection x ray fluorescence analysis (TXRF).Except the TiN sample, cerium do not detected in the sample after processing.About the TiN sample, after peeling off program, the second portion resist removes cerium, and described second portion resist is peeled off program and was approximately formed in 5 to 15 minutes by soaking in cold sulfuric acid.

Table 3

Fig. 3 is scanning electron microscopy (SEM) image, with white line draw outstanding SOI wafer 300 approximately under 65 ℃ at about 20%CNA with after approximately soaking approximately 30 minutes in the solution of 80%DI water, the border between the layer of the cross section of described wafer.The SOI wafer comprise body silicon substrate 330, with the silicon dioxide (SiO of body silicon substrate 330 adjacency ₂) insulating barrier 320 and with the upper silicon layer 310 of insulating barrier 320 adjacency.Before soaking, the thickness of upper silicon layer 310 is nominal (approximately) 70nm.After soaking, the thickness that records upper silicon layer 310 by SEM is about 69.22nm.Therefore, after soaking in CAN solution, SOI wafer or the layer that is included in the SOI wafer do not have measurable attenuation.

Fig. 4 has shown that SOI wafer 300 soaks in the described CAN solution with reference to figure 3 after, the XPS analysis result of described wafer.In conjunction with can be at the about leftmost peak between 103 and 104 electron-volts (EV) corresponding to SiO ₂In conjunction with can be at the about rightmost peak between 99 and 101 electron-volts corresponding to Si.Trace 410 representative contrasts, the wafer before namely soaking in CAN solution.Wafer after trace 420 representatives are soaked.

At least a portion of the technology of the present invention, the technology of for example drawing in Fig. 1-4 can be implemented in one or more integrated circuits.In forming integrated circuit, the design producing tube core to repeat on semiconductor wafer surface typically.Cut out or be cut into singulated dies from wafer, then be packaged into integrated circuit.One skilled in the art will recognize that how cutting crystal wafer and package die are to produce integrated circuit.The integrated circuit that manufactures like this is considered to a part of the present invention.

Fig. 5 has described according to embodiment of the present invention, the viewgraph of cross-section of the integrated circuit 500 of encapsulation.Tube core 504 and plastic packaging molds 508 that the integrated circuit 500 of encapsulation comprises lead frame 502, is connected with lead frame.Although Fig. 5 has only shown the integrated antenna package of a type, the present invention is not subjected to such restriction; The present invention can comprise the integrated circuit lead of enclosing with any encapsulated type.

Tube core 504 comprises herein the device of describing, for example FET or other electronic device of forming according to the inventive method, and can comprise other structure or circuit.For example, tube core 504 can comprise source region, drain region or the channel region of at least one conductor, MEM device, FET, FET or the grid conductor of FET, and their formation comprises by method of the present invention removes resist.

Embodiment B

Described and used solution of the present invention to remove the execution mode of the method for resist with batch mode.Specifically, the method of removing masking material has been described, described method comprises masking material and following contacting: (a) optional preliminary treatment, and then DI water cleans, the solution that comprises cerium of (b) describing herein, then DI water cleans, (c) sulfuric acid reprocessing, (d) DI water cleans, (e) rare standard clean solution 1(SC-1) process, (f) DI water cleans, and (g) IPA is dry.Optional preliminary treatment (a) and the condition of reprocessing (c) are included in approximately 20 to approximately 70 ℃, more preferably from about 40 use sulfuric acid and solvent for example tetraethyleneglycol dimethyl ether (tetraglyme) or lasting approximately 5 to about time of 45 minutes of gamma-butyrolacton to the about temperature of 50 ℃.During use, the concentration of sulfuric acid is preferably approximately 80% to about 100% scope.Contain the relevant condition of cerium solution (b) processing to use and be described in herein, and can easily be determined by those skilled in the art.For example, the processing that contains cerium can be included in approximately uses cerium compound concentration to be approximately 15 to about 25wt%(for example approximately 15 to about 25wt%CAN at 60 temperature to about 80 ℃ of scopes) solution approximately 15 to approximately 90 minutes.Rare SC-1 processes to be included in the about room temperature temperature to about 50 ℃ of scopes and continues approximately 1 to 20 minute, preferred approximately 1 to approximately 2 minutes.The example of rare SC-1 is concentrated ammonia liquor, dense H ₂O ₂, and the DI water solution of 1:1:40 by volume.Various water clean and preferably include 1 to 10 cleaning frequency, preferred approximately 3 to about 5 cleaning frequencies.

For single-wafer instrument or the instrument of spraying in batch, can be used for accelerating stripping process such as the variable of flow velocity, expulsion pressure and mechanical force.For example, after identical process was provided for batch mode, the time limit will be at low side or lower, and for example for optional preliminary treatment and post-processing step approximately 0.5 to approximately 1 minute, for the processing that contains cerium solution approximately 1 minute, rare SC-1 processed approximately 0.5 minute.

Embodiment C

In strongly acidic solution, Mn (II) forms permanganate (Mn (VII)) with Ce (IV) reaction very fast according to following reaction equation in well-beaten solution:

Mn(NO ₃) ₂·4H ₂O+5(NH ₄) ₂Ce(NO ₃) ₆→

10NH ₄NO ₃+4Ce(NO ₃) ₃+Ce(NO ₃) ₂(MnO ₄)+8NHO ₃

Advantageously, the permanganate that is reacted might regenerate by Ce (IV) ion.

Carry out experiment, wherein will implant under energy at 25keV is 1x10 with dosage ¹⁶/ cm ²The resist sample implanted of As contact 20 minutes with preparation A-D under 65 ℃, sulfuric acid cleaned 15 minutes at room temperature then.Significantly, pre-treatment step is not included, make and find out more easily whether add Mn influential.But imagined pre-treatment step at this.

Preparation A:20wt%CAN, the dense HNO of 3wt% ₃, 77wt%DI water

Preparation B:20wt%CAN, the dense HNO of 3wt% ₃, 0.1wt%Mn (NO ₃) ₂4H ₂O(～200ppm Mn), 76.9wt%DI water

Formulation C:20wt%CAN, the dense HNO of 3wt% ₃, 0.3wt%Mn (NO ₃) ₂4H ₂O, 76.7wt%DI water

Preparation D:20wt%CAN, the dense HNO of 3wt% ₃, 1wt%Mn (NO ₃) ₂4H ₂O, 76wt%DI water

No matter find concentration how, the existence of manganese all improves the implanted ions resist, particularly is difficult to the peeling off of major part (features) of removal separately with preparation A.In fact, be low to moderate 20ppm manganese in preparation A peeling off of resist of high density implantation had Beneficial Effect, yet, be preferred at least about 60ppm Mn in preparation A, to guarantee basically to remove resist (based on the light microscope analysis) fully.Importantly, in preparation A under the condition of 60ppm Mn, TiN corrosion rate in experimental error with the condition that does not have Mn under identical.

Carry out another group experiment, high dose implantation resist sample that wherein will be proprietary contacts 30-60 minute with preparation E-G under 70 ℃, then 40 ℃ of lower sulfuric acid cleaned 10 minutes.Significantly, pre-treatment step is not included, make and find out more easily whether add Mn influential.But imagined pre-treatment step at this.

Preparation E:20wt%CAN, 4wt%ATFA, 76wt%DI water

Preparation F:20wt%CAN, 4wt%ATFA is from Mn (NO ₃) ₂4H ₂The 20ppmMn of O, all the other are DI water

Preparation G:20wt%CAN, 4wt%ATFA is from Mn (NO ₃) ₂4H ₂The 60ppm Mn of O, all the other are DI water

In each situation, the preparation that comprises Mn is more effectively removed residue than the preparation that does not contain Mn.

Embodiment D

Carry out experiment, wherein will implant under energy at 25keV is 1x10 with dosage ¹⁶/ cm ²The resist sample implanted of As contact 10 minutes with sulfur acid pretreatment under 40 ℃, then contact 50 minutes with preparation H with I under 70 ℃, then 40 ℃ of lower sulfuric acid cleaned 10 minutes.

Preparation H:20wt%CAN, 6wt%ATFA, 73wt%DI water

Preparation I:20wt%CAN, 6wt%ATFA is from Mn (NO ₃) ₂4H ₂The 50ppmMn of O, all the other are DI water

After cleaning solution, with the trial zone optical imagery, and based on the graded reporting result of concrete test mask position.Each position has different character, such as spacing, thickness, area etc.Report the result with numeral, wherein " 10 " mean cleaning fully, and " 0 " means not cleaning.Can see result in Fig. 6.Can find out, the position that preparation H is invalid, in preparation I, the existence of manganese has significantly improved the cleaning of wafer.

The beyond thought subsidiary benefit of some complementary oxidants is that Treatment Solution stability to antisolvent precipitation under treatment temperature (70-80 ℃) increases.Join 50-100ppm Mn in various CAN+ATFA preparations by using as the manganese nitrate tetrahydrate, first observed has been extended 10-30% to the time of muddiness.Similarly, be added in orthoperiodic acid (H in the 200-2000ppm scope in the preparation E ₅IO ₆) make first observed arrive the scope of the muddy corresponding approximately 10-40% of time lengthening.

Embodiment E

Find unexpectedly, the CAN of higher concentration has improved the stability to antisolvent precipitation, for example from for for 20%CAN under 70 ℃ ~ 30 minutes to 27 hours for 50%CAN, but concentration and higher to the stability of antisolvent precipitation, the validity of peeling off is lower.As compromise, can add approximately 2-4wt%ATFA in 20-25wt%CAN, the bath life-span under 70 ℃ increased to greater than 8 hours.Adversely, under this temperature and concentration, to peel off in order reaching the resist (3.5E15As, 25keV) that medium high dose is implanted fully, to need to process greater than 2 hours under wet experimental bench environment, this causes the very high cost that has.

Consider based on these, need not any stabilizer have prepared one group 1, the aqueous solution of 3 and 5 % by weight CAN, and it is heated to 90-95 ℃ in the opening flask.1% and 3% solution showed after ~ 70 minutes without precipitation, and 5% solution began precipitation after ~ 20 minutes.In more controlled experiment, do not contain the solution of 5 % by weight CAN of stabilizer by adding solid CAN to prepare in the 250ml conical flask in the boiling DI water that stirred.Solution was boiled (~ 100 ℃) approximately 20 minutes, remain without the precipitation.

In another group experiment, the processing of the sample of implanting with 248nm resist patterning and with 3.5E15As, 25keV is as follows:

1. at 50 ℃ of H ₂SO ₄In 2 minutes

2. at 90-95 ℃ of solution that contains 0,1,3 or 5 % by weight CAN and in by the 5 % by weight CAN solution (being called " 5b ") that boil preparation in 15 minutes 15 minutes

3. at 50 ℃ of H ₂SO ₄In 20 minutes

The visual examination sample is obviously found out, for 5%CAN and may be for 3%CAN, the clean-up performance of layer is better than 20-25%CAN solution in the clean-up performance (see figure 7) of even typically seeing after 60 minutes under 70 ℃.What is interesting is, with the CAN solution of 5% boiling, the large resist layer of A and C is only after 5-7 minute and at final H ₂SO ₄Show cleaned before processing.More tiny part also shows cleaning usually, but many in them need last H really ₂SO ₄Clean.

Although do not wish to be subject to theoretical constraint, the result of these experiments shows, has best CAN concentration, and for example less than approximately＜10 % by weight CAN, the CAN concentration of described the best is peeled off height active combining with rational stability and be need not to use stabilizer.

Embodiment F

This experiment relates to ammonia and TFA concentration near central value (2%ATFA)+and/-15% change to be to form in position ATFA.Find unexpectedly, with NH ₃Compare with the solution (8-9 hour) that the TFA mol ratio is 1:1, the ammonia relative concentration has the much higher stability to antisolvent precipitation (for example〉13 hour) in the solution of TFA much higher (for example mol ratio is greater than 1:1, preferred 2:1 to 3:1) under 70 ℃.A few minutes after acutely jolting, the of short duration sediment that forms when mixing at first disappears.

Designed further experiment, eliminated thus the formation of ATFA, because AFTA does not help peeling off of masking material.Mix the sample that comprises ammonia and CAN in the 15mL plastic centrifuge tube.Attend by and jolt, all solution are all clarified in less than 5 minutes.Except as otherwise noted, bathing temperature is 81-81.5 ℃, and the temperature in developmental tube is 75-76 ℃.Measure precipitation with absorbance measuring.Record and have NH ₃/ CAN ~ 1.61:1(mole) 25%CAN solution kept 9.7 hours under 75 ℃, and under ~ 95 ℃ extra the maintenance 7 hours.What is interesting is, stability increases the CAN solution that is not limited to high concentration.When using DI water with NH ₃/ CAN〉1:1(mole) five times of 25 % by weight CAN solution dilutions during to final 5%CAN, the solution after dilution remains clarification, then keeps under ~ 95 ℃ without precipitation 5 hours.The result of stability test is as shown in table 4.

Table 4: have various NH ₃The solution of/CAN ratio is along with the stability of time

The ammonia solution of preparation high concentration, the peeling off of following execution masking material.Substrate and the H that will comprise masking material ₂SO ₄Contact is 10 minutes under 54 ℃.Then substrate is contacted 1 hour with corresponding solution under 70 ℃.Then use H ₂SO ₄Cleaned substrate 10 minutes after under 54 ℃.Obtained the bright spot image, wherein bright spot has consisted of remaining photoresist.Result is presented in Fig. 8 and 9, and wherein Fig. 8 and 9 corresponds respectively to and NH ₃The solution that is 1.002:1 and 3.826:1 with the TFA mol ratio contacts.Each image represents the position, hole on the F20 plate, and therefore, the result of each solution shows four parts.

Should recognize, form according to the present invention described in literary composition and demonstration integrated circuit and integrated circuit package in the drawings can be used for application, hardware and/or electronic system, such as one or more digital computers with associated internal memory, enforcement specificity integrated circuit, functional circuit etc.Be used for comprising or using other suitable hardware of parts of the present invention and system can include but not limited to personal computer, communication network, e-commerce system, portable communication apparatus (for example mobile phone) and solid state medium storage device.System and the hardware of having included this integrated circuit in are considered to a part of the present invention.In view of the instruction of the present invention that provides in literary composition, those of ordinary skills can dream up other enforcement and the application of the technology of the present invention.

Note, embodiments of the present invention also are applicable to remove and peel off the photoresist that there is no implanted ions or there is no at least serious implanted ions.This photoresist comprises the photoresist that may be insoluble to conventional organic solvent, for example because crosslinked polymer causes the negative photoresist that is insoluble to conventional organic solvent.Can use technology of the present invention to remove or peel off this photoresist.

To recognize and should be understood that and to realize the illustrative embodiments of the invention described above with multiple different mode.In view of the instruction of the present invention that provides in literary composition, those of ordinary skill in the related art can dream up other implementation of the present invention.In fact, although described in this article Illustrative execution mode of the present invention with reference to accompanying drawing, but should be understood that to the invention is not restricted to those accurate execution modes, those skilled in the art can make multiple other variation and modification not departing under scope of the present invention or spirit.

Claims

1. be used for to remove the method for masking material, described method comprises the solution of described masking material with at least a other oxidant that comprises cerium compound, water and choose wantonly is contacted.

2. the process of claim 1 wherein and comprise cerium in salt or co-ordination complex.

3. the method for claim 2, wherein said salt is ammonium ceric nitrate Ce (NH ₄) ₂(NO ₃) ₆(CAN).

4. the method for claim 2, wherein said salt are following at least a: cerous nitrate, Cericammoniumsulfate, cerous sulfate, cerous hydrosulfate, perchloric acid cerium, methanesulfonic acid cerium, trifluoromethanesulfonic acid cerium, cerium chloride, cerium hydroxide, carboxylic acid cerium, beta-diketon cerium, trifluoroacetic acid cerium and cerous acetate.

5. the method for the claims any one, wherein said solution also comprises at least a stabilizer.

6. the method for claim 5, wherein said at least a stabilizer comprises the ammonium salt that is selected from ammonium chloride, ammonium hydroxide, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, carboxylic acid ammonium, beta-diketon ammonium, ammonium acetate, ammonium perchlorate, trifluoroacetic acid ammonium, methanesulfonic acid ammonium and trifluoromethanesulfacid acid ammonium.

7. the method for claim 5, wherein at least a stabilizer comprises the trifluoroacetic acid ammonium.

8. the method for claim 7, wherein pass through ammonia and trifluoroacetic acid combination producing trifluoroacetic acid ammonium.

9. the method for claim 8, wherein the mol ratio of ammonia and trifluoroacetic acid at about 0.8:1 to the scope of about 5:1.

10. the method for the claims any one, wherein solution comprises CAN and ammonia.

11. the method for claim 10, wherein the mol ratio of ammonia and CAN at about 1:1 to the scope of about 2:1.

12. right is wanted 5 method, wherein at least a stabilizer comprises at least a acid that is selected from perchloric acid, glacial acetic acid, nitric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, periodic acid, trifluoroacetic acid, hydrochloric acid and polystyrolsulfon acid.

13. the method for the claims any one, wherein said solution comprise based on total solution weight approximately 0.01 to the about CAN of 70 % by weight.

14. the method for the claims any one, wherein said solution comprise based on total solution weight approximately 20 to the about CAN of 30 % by weight.

15. the method for the claims any one, wherein said solution comprise based on the about CAN of 1 to 8 % by weight of total solution weight.

16. the method for the claims any one, it comprises at least a other oxidant that is selected from manganese, ruthenium, osmium, iridium and combination thereof.

17. the method for the claims any one, it comprises and is selected from RuO ₄, OsO ₄, KMnO ₄, NH ₄MnO ₄, RuCl ₃, OsCl ₃, Ru (NO ₃) ₃, Os (NO ₃) ₃, Mn (NO ₃) ₂XH ₂O, MnCO ₃, MnSO ₄XH ₂O, Mn (C ₂H ₃O ₂) ₂XH ₂O, MnCl ₂, MnBr ₂, and the combination at least a other oxidant.

18. the method for the claims any one, it comprises at least a other oxidant, and described at least a other oxidant comprises Mn (NO ₃) ₂XH ₂O。

19. the method for the claims any one, wherein when solution contact masking material, the temperature of solution is approximately 35 and approximately between 90 degrees centigrade.

20. the method for the claims any one, wherein with masking material with before solution contacts, masking material is by at least a below implanted ions: (i) greater than about 5x10 ¹⁴Ion/square centimeter; (ii) before ion affects masking material the average energy of ion greater than about 5000 electron-volts of (〉 5KeV).

21. the method for the claims any one, wherein substrate comprises titanium nitride.

22. electronic device, it forms by masking material is contacted the removal masking material with the solution of at least a other oxidant that comprises cerium, water and choose wantonly.

23. the electronic device of claim 22 wherein will comprise cerium in salt or co-ordination complex.

24. the electronic device of claim 23, wherein said salt are ammonium ceric nitrate Ce (NH ₄) ₂(NO ₃) ₆

25. the electronic device of claim 23, wherein said salt are following at least a: cerous nitrate, Cericammoniumsulfate, cerous sulfate, cerous hydrosulfate, perchloric acid cerium, methanesulfonic acid cerium, trifluoromethanesulfonic acid cerium, cerium chloride, cerium hydroxide, carboxylic acid cerium, beta-diketon cerium, trifluoroacetic acid cerium and cerous acetate.

26. the electronic device of claim 22-25 any one, it comprises at least a other oxidant that is selected from manganese, ruthenium, osmium, iridium and combination thereof.

27. the electronic device of claim 22-25 any one, it comprises and is selected from RuO ₄, OsO ₄, KMnO ₄, NH ₄MnO ₄, RuCl ₃, OsCl ₃, Ru (NO ₃) ₃, Os (NO ₃) ₃, Mn (NO ₃) ₂XH ₂O, MnCO ₃, MnSO ₄XH ₂O, Mn (C ₂H ₃O ₂) ₂XH ₂O, MnCl ₂, MnBr ₂, and the combination at least a other oxidant.

28. the electronic device of claim 22-27 any one, wherein electronic device comprises integrated circuit.

29. the electronic device of claim 22-28 any one, it comprises following at least a: (i) transistor; (ii) comprise the transistor of metal gate; (iii) comprise the transistor of titanium nitride; (iv) integrated circuit; (v) microelectronic mechanical devices.

30. the electronic device of claim 22-29 any one, it comprises following at least a: (i) silicon layer and silicon dioxide (SiO ₂) layer; (ii) titanium nitride (TiN) layer; The transistorized source region of (iii) implanting with dopant ions; The transistorized drain region of (iv) implanting with dopant ions; The transistorized channel region of (v) implanting with dopant ions.

31. form the method for electronic device, described method comprises:

Formation comprises the substrate of titanium nitride;

In order to the lower at least a implanted ions photoresist that comes: (i) greater than about 5x10 ¹⁴Ion/square centimeter; (ii) before ion affects photoresist the average energy of ion greater than about 5000 electron-volts of (〉 5KeV); With

With photoresist with contact with the solution that comprises cerium, water and optional at least a other oxidant.

32. the method for claim 31, wherein said electronic device comprises following at least a: (i) transistor; (ii) comprise the transistor of metal gate; (iii) comprise the transistor of titanium nitride; (iv) integrated circuit; (v) microelectronic mechanical devices.

33. the method for claim 31 or 32 wherein comprises cerium in salt or co-ordination complex.

34. the method for claim 31 or 32, wherein salt is ammonium ceric nitrate Ce (NH ₄) ₂(NO ₃) ₆