TWI529794B - Etch resistant alumina based coatings - Google Patents

Description

Anti-etching alumina-based coating film

The following disclosure relates to the fabrication of microelectronic devices, and in particular (but not exclusively) to layers that are capable of forming structures on a substrate using photolithography. In particular, the present invention relates to methods of fabricating materials and coating films useful in photolithographic applications and subsequent etching processes to form desired structures on substrates, and applications thereof.

In order to meet the demand for smaller electronic products, there is an ongoing effort to increase the performance of packaged microelectronic devices while minimizing the area of the devices on the printed circuit board.

In the current miniaturization, it is difficult to reduce the height of the high-performance device and the surface area size (ie, density). One method of increasing the density of components of a microelectronic device in addition to reducing the line width is to place one device or an integrated circuit (IC) on the other. In practice, this is accomplished by electrically coupling the active circuit layer on the die to another active circuit layer on the same or different die by a through substrate via. In the semiconductor industry, the latter is most commonly referred to as through silicon via (TSV).

These vertical interconnects electrically couple bond pads or other conductive elements adjacent or adjacent to one side of the die to conductive elements adjacent or adjacent to the other side of the die. For example, via a back-end-of-the-line (BEOL) or a "via last method", via a germanium wafer interconnect process (for example) by backing from the wafer Bonding pad to the front Deep vias are formed for construction, and the wafer contains most of the circuitry for a particular design. The vias are often closed at one end, then filled with a conductive material, and further processed in the fabrication process, and finally thinned to reduce the thickness of the final die, sufficient to achieve a through substrate interconnection. Through-front-end-of-the-line (FEOL) or "via first method" processing, vias are formed to a large extent before the design circuit is fabricated. The "back via method" is more challenging because, in general, the vias are much deeper than the vias produced by the "first via method", and the formation of such vias includes etching or laser Processing through a layer stack such as tantalum and tantalum oxide.

The complexity of forming a through-substrate interconnect is that it is difficult to perform etching to create such a deep narrow hole in the substrate. These high aspect ratio vias are often formed on a 0.75-1.5 mm thick substrate and should exhibit minimal sidewall roughness to allow subsequent fabrication steps to be successful. The closed vias can be formed by etching holes through a pattern created by photolithography. The etching is mainly performed in an inductive coupled plasma (ICP) reactor in which the conditions for forming the via holes may require a large amount of time. In addition, the depth of the holes is difficult to control and the etchant may damage features on the substrate unless properly protected.

The via holes can also be formed by laser processing holes in the substrate. Laser processing of high aspect ratio vias through the substrate is not suitable for many applications. The depth of the hole is difficult to control, resulting in a shallow or too deep through hole. Laser processing is also a high temperature process that creates a hot zone that can affect adjacent structures in the wafer and requires removal of the resulting residue. Therefore, the etching or laser processing in the substrate is deep Aspect ratio holes can be difficult in many applications.

A second complication of forming a deep high aspect ratio structure is the pattern integrity of the structure. Patterning of a particular layer is often performed by a multi-step process consisting of photoresist spin coating, photoresist exposure, photoresist development, substrate etching, and photoresist removal. Execution of deep via etch may require extremely thick photoresist during etching as the environment may also cause undue degradation of the photoresist. Therefore, the difference in etching rate between the substrate to be etched and the coating film for preventing improper etching of the substrate should be as large as possible. Additionally, coating the thick resist may be impractical depending on the time consumed and contamination of the ICP reactor caused by the use of the thick resist. Therefore, it is important to etch the resist for patterning and the selectivity of the substrate.

In addition, materials with high etch selectivity or hard masks have been used in the formation of photolithography with features of line widths of 65 nm and below. Since the change in line width of the pattern during photolithography can be caused by optical interference of light reflected off the underlying layer on the semiconductor substrate, an anti-reflective coating (ARC) is used to avoid this effect. In order to minimize the number of processing steps required, it is beneficial to combine the properties of the hard mask layer with the ARC in a single layer. Regarding the state of the art, reference is made to U.S. Patent Application Serial No. 2008/0206578.

In view of the shortcomings of prior art in patterning and etching materials to enable the formation of deep high aspect ratio structures and narrow line widths, there is a continuing need to develop novel materials that substantially reduce degradation of the patterned material and improve the display on the substrate. The design protects and improves the deep aspect ratio and the manufacturing efficiency and control of other through holes, holes and structures.

It is an object of the present invention to provide a novel composition for applications requiring a highly etch-resistant hard mask that sufficiently maintains its thickness and properties in an environment for etching a desired substrate in a semiconductor fabrication process.

Another object of the present invention is to provide a novel material composition based on an alumina polymer and a copolymer of aluminum and an organic cerium oxide, which meets the requirements of a hard mask.

Another object of the present invention is to provide a method of preparing a hard mask coating film on a substrate.

A fourth object of the present invention is to provide a solvent system which stabilizes the alumina polymer and the copolymer of aluminum and organic cerium oxide sufficient to allow for a longer shelf life without unduly limiting its performance.

Another object is to provide a hard mask of the present invention that also acts as an anti-reflective coating and a hard mask (etch mask) in semiconductor or especially TSV processes. According to the innovative anti-reflective coating, the hard mask also acts as a bottom anti-reflective coating.

A further object is to provide a layer in an integrated circuit having a coefficient of thermal expansion (CTE) value close to 矽.

Finally, it is an object to provide a material that has such good optical properties that it will enable good lithography and non-sacrificial properties of the film, which means that the hard mask can have a permanent optical function in the device.

This and other objects are claimed and described herein, which are achieved by the present invention in conjunction with existing materials and methods.

The invention is based on forming a guarantee on a substrate in a semiconductor etching process The viewpoint of a protective hard mask layer comprising the step of applying a solution or a colloidal dispersion of an alumina polymer onto the substrate by solution deposition, the solution or dispersion being by water and a catalyst Obtained by hydrolyzing and condensing a monomer of at least one alumina precursor in a solvent or solvent mixture in the presence.

In particular, preferred alumina precursors have the general formula AlX _n (OR ¹ ) _3-n

Wherein R ¹ is independently selected from the group consisting of hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; X is independently a chloro group, a bromo group, an iodine group, an ester group, and especially an anthracene. Selected from the group consisting of a sulfhydryl group, a thio group, and a nitro group; n is an integer between 0 and 3; or (R ² ) _m AlX _n (OR ¹ ) _2-n

Wherein R ¹ is independently selected from the group consisting of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; and R ² is independently a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, β- Selected from the group of diketones, esters, and β-ketoesters.

More specifically, the main feature of the present invention is the content described in the characterizing portion of the first aspect.

The invention achieves considerable advantages. Accordingly, various embodiments of the present invention are suitable for fabricating a hard mask on a semiconductor substrate in a TSV process A high aspect ratio via structure is formed. Furthermore, the coating comprises providing a hard mask in the manufacture of the MEMS and performing it in the form of an anti-reflective coating in photolithographic patterning. The materials of the present invention can also be used to provide hard masks and anti-reflective coatings in the fabrication of dual damascene interconnects.

Subsequently, the invention will be examined more closely with the aid of the embodiments, with reference to the accompanying drawings.

Based on the above discussion, the preferred embodiment encompasses a preparation solution of a novel alumina polymer and a copolymer of an organic siloxane and alumina which can be used in the manufacture of a hard mask film in a conventional semiconductor process.

The composition is synthesized from a variety of inorganic or organoaluminum precursors. The composition may also optionally comprise an organodecane precursor copolymerized with an aluminum precursor.

The composition of the material can be selected such that the material from which it is produced can be patterned or absorbed by conventional photolithography techniques using light of the desired wavelength used in the photolithographic process.

The material is prepared by reacting an aluminum-containing precursor with a solvent which causes hydrolysis and condensation of the precursor to produce an oligomeric and polymeric substance in a solvent.

According to one embodiment, a plurality of different precursors (more than one) are used, which allows for greater flexibility in adjusting the material properties that are more suitable for the application.

The material obtained can be peptized using a mineral acid or an organic acid, a β-diketone or a β-diketone ester material to impart improved storage stability in a solution state.

The main chain of the formed alumina polymeric material is composed of repeating units -Al-O-group It may be interrupted by an organic acid or a β-diketone-derived ligand coordinated to aluminum as the case may be.

According to a preferred embodiment, the above-described composition can be used as a hard mask in the manufacture of semiconductors. It will have a high content of aluminum (atoms).

Further, the material may be peptized using an organic acid, β-diketone or β-diketone ester material having a functional group which can be activated by exposure after deposition, thereby allowing photolithography to be used by photolithography. The hard mask material is patterned.

Alternatively, the material may be peptized using an organic acid, beta-diketone or beta-diketone ester material having a functional group that absorbs light (193-460 nm) used in photolithography applications, thereby allowing materials Used in applications where an anti-reflective coating is required. Therefore, the main chain of the formed alumina polymeric material is composed of a repeating unit -Al-O- mixed with a functional group derived from a colloidal solvent.

The material can be further prepared by reacting the above-described aluminum precursor and organic ruthenium precursor in a solvent with water which causes hydrolysis and condensation of the precursor to produce oligomerization and polymeraceous matter.

The use of an organic germanium precursor with a functional group that can be activated by exposure after deposition allows the hard mask material to be patterned. Similarly, the use of organic germanium precursors with groups of light that absorbs wavelengths (193-460 nm) used in photolithography applications allows materials to be used in applications requiring antireflective coatings.

Thus, the backbone of the formed alumina polymeric material is miscible with the peptizer (β-diketone, β-diketone or organic acid) mentioned for the aluminum precursor and the organic substituent on the decane precursor. Repeat unit - Al-O- and -Si-O- composition.

The resulting solution containing the reaction product recovered from the precursor reaction can then be applied to the semiconductor device as a hard mask layer in a standard lithography manufacturing process.

The method of applying the solution in a wide variety of semiconductor applications, and particularly in lithography processes, consists of the following:

1. Applying a solution to the surface of a semiconductor component or substrate by means of spin coating, slit coating, spray coating, roll coating or other coating technique for depositing material in a liquid phase.

2. The coating film is optionally patterned by exposing the dried coating film to light of a selected wavelength through a mask and developing the non-exposed areas.

3. Curing the applied layer to obtain a hard mask in a single layer. The lithography process is then carried out, in which other layers need to be constructed in a given device.

Turning now to a preferred precursor, it can be noted that in one embodiment, a precursor having the following general formula (hereinafter "Precursor 1") is used.

AlX _n (OR ¹ ) _3-n

Wherein R ¹ is independently selected from the group consisting of hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; X is independently a chloro group, a bromo group, an iodine group, an ester group, and especially an anthracene. Selected from the group consisting of a base, a sulfate group, a sulfur group, and a nitro group; n is an integer between 0 and 3.

Further assuming that in the case of n=3, such as hydrate is also included And a complex of ether complexes.

In the second embodiment, another precursor having the following general formula (hereinafter referred to as "precursor 2") is used.

(R ² ) _m AlX _n (OR ¹ ) _2-n

Wherein R ¹ is independently selected from the group consisting of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an aryl group; and R ² is independently a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, β- Selected from the group of diketones, esters, and β-ketoesters; X is independently selected from the group consisting of a chloro group, a bromo group, an iodine group, an ester group, especially a thiol group, a sulfate group, a thio group, and a nitro group. And m is an integer between 0 and 2; and n is an integer determined by 3-m.

It is further assumed that in the case of m = 0, a complex such as a hydrate and an ether complex is also included.

In the third embodiment, a precursor having the following general formula (hereinafter referred to as "precursor 3") is used.

(R ³ ) _k -Si-X _4-k

Wherein R ³ is independently from linear alkyl, branched alkyl, cyclic alkyl, alkenyl (linear, cyclic, and branched), alkynyl, epoxy, acrylate, alkyl acrylate a heterocyclic group, a heteroaromatic group, an aromatic group (consisting of 1 to 6 rings), an alkylaromatic group (consisting of 1 to 6 rings), a cyanoalkyl group, an isocyanatoalkyl group, an amine Selected from the group of alkyl, sulfalkyl, alkyl urethane, alkyl urea, alkoxy, decyloxy, hydroxy, hydrogen, and chloro-functional groups, at least one R ³ being the precursor a group acting as a functional group reactive when a latent photoactive catalyst is activated; X is independently selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, a chloro group, a bromo group, an iodine group, and an alkylamine group; And n is an integer between 0 and 3.

The reaction product obtained by polymerization or copolymerization using one or more of the above precursors by hydrolysis will have a composition consisting of the above precursors 1-3 (in which the integer n = 1), and the composition consists of the following repeating units. General formula: -[Al-O _1.5 ] _a -[(R ² ) _m -Al-O-] _b -[(R ³ ) _k -Si-O _2/3 ] _c -

Wherein R ² and R ³ have the same meanings as above, and a, b and c are values based on the relative molar ratios of the precursors 1-3 for obtaining the above composition.

The resulting hard mask coating composition has excellent etching performance after photoresist development. High aluminum content is preferred for each use.

In the case where the organodecane precursor is used as a comonomer in the hydrolysis and condensation of the material, a trade off exists to obtain a coating film exhibiting sufficient etching selectivity and a material that can be patterned using photolithography. Therefore, in practice, 20% to 95% of the Al content is preferable and 40% to 90% of the Al content is more preferable.

To tailor the properties of the preferred composition, precursors 1 through 3 can be selected such that: - a precursor will provide sufficient etch selectivity compared to the substrate forming the deep via and thus protect the area of the substrate covered by it; - a precursor will provide sufficient shelf life and be used to control the molecular weight of the resulting composition; A precursor will provide sufficient adhesion to the substrate forming the deep via; - a precursor will provide a functional group that can be activated by a latent catalyst capable of patterning the material using photolithography; and - a precursor The material will provide a functional group capable of absorbing light of the wavelengths used in photolithographic applications.

More specifically, the group R ¹ may be selected from the group of organic substituents selected from C _1-12 alkyl groups which may be present in the alkoxy, cyano, amine, ester or carbonyl functional groups. The alkyl group may optionally be halogenated with at least one halogen atom (fluoro, chloro, bromo or iodo). The alkyl group may be a straight chain, a branched chain or a cyclic type. The precursor containing the above group is preferably purified by distillation. In particular, shorter alkyl chains containing from 1 to 6 carbon atoms are preferred. An alkyl chain having 1 to 4 carbon atoms is preferred.

The group R ² may be selected from the group of carboxylic acids, α-hydroxycarboxylic acids, carboxylates, β-diketones, esters or β-ketoesters, and C _1-12 may be present in the halogen, unsaturated and aromatic functional groups. alkyl. The precursor 2 containing the above group may preferably be purified by distillation or prepared so that the total metal ion content is less than 500 ppb, preferably less than 50 ppb. In particular, an alkyl chain having 3 to 7 carbon atoms as short as possible is preferred.

An alkyl chain having 4 to 6 carbon atoms is preferred. Better for organic Examples of acids, beta-diketones or beta-diketone esters which also contain functional groups which can be polymerized using photolithographic techniques (such as acrylonitrile, alkyl propylene sulfonyl, acrylate, alkyl acrylate) The composition of the compound of the group and the epoxy functional group). The functional compound may contain from 5 to 12 carbon atoms. An alkyl chain having 6 to 10 carbon atoms is more preferred. The preferred embodiment also includes an organic acid, a β-diketone or a β-diketonate containing a functional group capable of absorbing light of a wavelength used in photolithography. Particularly preferred light absorbing examples are aromatic or polyaromatic (containing 2-6 aromatic rings) having at least one of the substituents being an organic acid, a beta-diketone or a beta-diketonate.

The group R ³ can be selected such that further reaction can be carried out during heating, allowing the material to be further densified (ie, crosslinked). More preferably, it is allowed to use such functional groups of a latent catalyst which can be activated in a standard lithography process to produce a patternable coating film. The substituent includes a C _1-12 alkenyl group, a C _1-12 alkynyl group, a C _1-12 acrylate group, a C _1-12 alkyl acrylate group, and a C _1-12 epoxy group. Preferred alkenyl and alkynyl groups consist of from 1 to 6 carbon atoms, such as ethenyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl , ethenyl, propargyl, butynyl, pentynyl and hexynyl. The propylene fluorenyl group, the alkyl propylene sulfhydryl group, the acrylate group, and the alkyl acrylate group substituent are preferably composed of 1 to 7 carbon atoms, which may be hetero atom-containing. More preferably, it is allowed to use such functional groups of a latent catalyst which can be activated in a standard lithography process to produce a patternable coating film. Preferred acrylate-based substituents contain methyl acrylate and ethyl acrylate. Preferred alkyl acrylate substituents consist of methyl methacrylate, ethyl methacrylate, ethyl methacrylate and ethyl ethacrylate. The epoxy substituent preferably consists of from 1 to 8 carbon atoms which may be heteroatomized. Preferred epoxy substituents are, for example, glycidoxypropyl and ethyl-(3,4-cyclohexyl epoxy). The use of a substituent containing a functional alkenyl group, an alkynyl group, an epoxy group, an acrylate group, and an alkyl acrylate group allows the material to be used in combination with a latent catalyst that can be activated by exposure to light of a desired wavelength. Light can pattern the material.

The group R ³ can also be selected such that the resulting reaction product has the ability to absorb light of the wavelengths used in photolithographic processing. The substituent includes a C _1-12 alkenyl group, a C _1-12 alkynyl group, a C _1-12 acrylate group, a C _1-12 alkyl acrylate group, a C ₆ -C ₃₆ aromatic group, and a C ₆ -C group. ₃₆ heteroaromatic groups. More preferred is an aromatic compound which can be purified by distillation. Preferred aromatic groups may contain substituents such as C _1-6 alkyl, C _1-6 fluorenyl, C _1-6 alkoxy, nitro, amine and halogen functional groups. Particularly preferred are groups which can be independently selected and used in combination to adjust the optical properties (such as refractive index and extinction coefficient) of the material at a desired wavelength after the material is cured on the semiconductor substrate.

Clear examples of compounds suitable for precursor 1 include aluminum hydroxide, aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum second butoxide, aluminum chloride (and other aluminum halides, including complexes thereof and hydration) , aluminum nitrate (including hydrates thereof), aluminum sulfate (including hydrates thereof), and a combination of alkoxy groups and aluminum halide precursors (such as aluminum chlorodisisopropoxide), and any other Other precursors that are readily composed of functional groups that are cleaved from aluminum during polycondensation.

A clear example of a suitable precursor 2 comprises the above-mentioned related aluminum precursor, wherein the organic group R ² is contained in the form of a covalent bond or via coordination. The compound is 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-propyl-2,4-pentanedione , 3,3-dimethyl-2,4-pentanedione, 3,5-heptanedione, 4-methyl-3,5-heptanedione, 4-ethyl-3,5-heptanedione , 4-propyl-3,5-heptanedione, 4,4-dimethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, 1-phenyl-1, 3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 3-chloro-2,4-pentanedione, 2-ethenylcyclopentanone, 2-ethenyl ring Hexanone, ethyl acetate, ethyl 2-methylacetate, ethyl 2-ethylacetate, ethyl acetate, ethyl acetate, methyl 3-oxovalerate , isopropyl acetate, isopropyl 2,4-dioxy valerate, methyl 3-oxohexanoate, methyl 4-methyl-3-oxo-pentanoate, ethyl ethane Allyl acetate, methyl 2-methyl-3-oxo-pent-4-enoate, methyl 4-methoxyacetate, 2-hydroxy-2-methyl-3-oxo Methyl butyrate, methyl 2-oxocyclopentanecarboxylate, methyl 2-oxocyclohexanecarboxylate, ethyl 2-oxocyclopentanecarboxylate, 2-oxocyclohexane Ethyl formate, ethyl 2-ethylacetate, 3-side Methyl heptyl group, acetyl isobutyl acetate, 4,4-dimethyl-3-oxo-pentanoate, ethyl isobutyl acyl, C _1-12 alkylcarboxylic acids, C _1-12 Unsaturated carboxylic acid and C _1-12 aromatic carboxylic acid.

A clear example of a suitable precursor 3 that can be activated using a latent photoactive catalyst comprises methacryloxypropyltrimethoxydecane, methacryloxypropyltriethoxydecane, methacryloxypropane Tris-propoxydecane, methacryloxypropyl propylene (isopropoxy) decane, methacryloxypropyltrichlorodecane, methacryloxypropylmethyldimethoxy Decane, methacryloxypropylmethyldiethoxydecane, propyleneoxypropyltrimethoxydecane, propyleneoxypropyltriethoxydecane, propyleneoxypropyltripropoxide Base decane, propylene methoxy propyl stilbene (isopropoxy) decane, propylene methoxy propyl trichloro decane, propylene methoxy propyl methyl 2 Methoxydecane, propylene methoxy propyl methyl diethoxy decane, methyl methacryloxypropyl trimethoxy decane, methyl methacryloxypropyl triethoxy decane, Methyl methacryloxypropyltripropoxy decane, methyl methacryloxypropyl propylene (isopropoxy) decane, methyl methacryloxypropyl trichloro decane, A Methyl propylene methoxy propyl methyl dimethoxy decane, methyl methacryloxypropyl methyl diethoxy decane, methacryloxypropyl trimethoxy decane, methyl Propylene methoxypropyltriethoxy decane, methacryloxypropyltripropoxydecane, methacryloxypropyl propylene (isopropoxy)decane, methacryloxypropane Trichlorodecane, methacryloxypropylmethyldimethoxydecane, methacryloxypropylmethyldiethoxydecane, glycidoxypropyltrimethoxydecane, glycidol Oxypropyl triethoxy decane, glycidoxypropyl tripropoxy decane, glycidoxypropyl ginseng (isopropoxy) decane, glycidol Propyltrichlorodecane, glycidoxypropylmethyldimethoxydecane, glycidoxypropylmethyldiethoxydecane, ethyl-(3,4-cyclohexylcyclooxy)trimethyl Oxydecane, ethyl-(3,4-cyclohexyl epoxy)triethoxydecane, ethyl-(3,4-cyclohexyl epoxy)tripropoxydecane, ethyl-(3, 4-cyclohexyl epoxy) tris(isopropoxy)decane, ethyl-(3,4-cyclohexyl epoxy)trichlorodecane, ethyl-(3,4-cyclohexyl epoxy)-methyl Dimethoxy decane and ethyl-(3,4-cyclohexyl epoxy)methyldiethoxy decane.

A clear example of a suitable precursor 3 that can be used to adjust the optical properties of the resulting material is phenyltrimethoxydecane, phenyltriethoxynonane, phenyltripropoxydecane, phenyl cis (isopropoxy)decane Phenyltrichloromethane, naphthalene Trimethoxy decane, naphthyltriethoxy decane, naphthyltripropoxydecane, naphthyl stilbene (isopropoxy)decane, naphthyltrichlorodecane, decyltrimethoxydecane, decyltriethyl Oxydecane, mercaptotripropoxydecane, decyl cis (isopropoxy) decane, decyl trichlorodecane, phenanthryl trimethoxy decane, phenanthryl triethoxy decane, phenanthryl tripropoxy Decane, phenanthryl (isopropoxy) decane, phenanthryl trichlorodecane, decyltrimethoxydecane, decyltriethoxydecane, decyltripropoxydecane, decyl hydrazine (isopropoxy) And decane, decyl trichloro decane, decyl trimethoxy decane, decyl triethoxy decane, decyl tripropoxy decane, decyl cis (isopropoxy) decane, and decyl trichloro decane. Such examples of aromatic substituents may be attached to the oxime at any position of the molecule (e.g., 1-naphthyl, 2-naphthyl) and may additionally carry, for example, an alkyl group, a decyl group, an alkoxy group, a nitrate on the aromatic ring. a functional group of a group, an amine group or a halogen atom.

The polymer obtained from the above-mentioned aluminum and decane precursor which are mutually hydrolyzable and copolymerizable and which contains a functional group which can be further reacted after activation of the latent photoactive catalyst produces a coating film which can be used as a hard mask in the photolithography process.

In general, the following are the functions of the precursor groups described above: Precursor 1 - provides a high aluminum content to the hard mask coating; Precursor 2 - gives a sufficient shelf life and optionally patterned contours obtained from standard lithography processes Or provide material light absorption function; Precursor 3 - gives the patterned contour obtained by standard lithography process, light absorption function.

A preferred composition based on the percentage of moles of the precursor used is: precursor 1:50-99; Precursor 2: 5-80; and precursor 3: 1-40.

Particularly preferred mole percentages are: precursor 1:50-90; precursor 2: 10-70; and precursor 3:5-30.

The preferred embodiment is produced by acid or base catalyzed hydrolysis and condensation of 1-4 aluminum precursors, preferably 1-2 aluminum precursors, optionally copolymerized with a decane precursor, in a solvent or solvent combination. The reaction proceeds. Suitable solvents for carrying out the hydrolysis and condensation steps are acetone, tetrahydrofuran, 2-methyltetrahydrofuran, butanone, cyclopentanone, cyclohexanone, alcohols (methanol, ethanol, propanol), propylene glycol derivatives [especially propylene glycol monomethyl ether) Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monopropyl ether (PNP) ], ethylene glycol derivatives and methyl tert-butyl ether. A mixture of two or more of these solvents may also be used. The weight ratio of solvent to precursor in the synthesis can range from 20:1 to 0.5:1. The weight of the solvent and the precursor is preferably in the range of 10:1 to 1:1. The acid or base catalyzed hydrolysis of the precursor and the amount of water used in the condensation reaction can vary significantly. Each hydrolyzed functional group uses from 1 to 3 moles of water to form a polymeric material, and a colloidal suspension of polycationic aluminum species is produced in a 5-15 fold excess by weight. For the preparation of the polymeric material, 1-2 moles of water based on the hydrolyzable functional group is preferred, and when preparing the colloidal polycationic aluminum material, a 5-10 excess by weight is preferred. The reaction mixture may be stirred at room temperature during the synthesis or refluxed for 1-48 hours, preferably 1-24 hours.

Once the hydrolysis and condensation reactions are completed, excess reagent (water), reaction by-products (such as methanol, ethanol, isopropanol, 2-butanol) and solvent can be removed under reduced pressure. During the removal of the volatile material, another solvent having a higher boiling point and a more desirable nature may be introduced depending on the use in the further manufacturing step of the polymer solution. Once the volatiles are removed, the resulting material can then be formulated into its final composition or subjected to a molecular weight adjustment step. This molecular weight increasing step is carried out at a high temperature range of 50 ° C to 180 ° C. More preferably, 60-120 ° C is used during the molecular weight adjustment step. After the molecular weight increase step, the material can be formulated into its final composition.

The formulation consists of using a solvent or a combination of such solvents to dilute the material. The solvent used in the final formulation is selected to maximize film uniformity and storage stability. For good spin-on properties, higher boiling and viscosity solvents may be preferred (e.g., PGMEA). A stabilizing solvent can be added to the product to improve storage stability. The solvent most typically has a hydroxyl group because these solvents coordinate with the polymeric OH or react with such polymeric OH without adversely affecting the properties of the cured film. Additives such as surfactants (from, for example, BYK-Chemie, 3M and Air Products), photolatent catalysts or thermal latent catalysts (such as Rhodorsil 2074 and Irgacure 819), as well as other peptizers, may be added. The surfactant can improve the wetting of the substrate to be coated and thus improve the uniformity of the resulting film. Generally, a nonionic surfactant is preferred. The peptizer provides a modified shelf life for the product. The peptizer may consist of an inorganic or organic acid or a beta diketone derivative.

After coating, drying, and curing, a film composed of an alumina or aluminoxane core having a carbon-based functional group is formed. The curing temperature is preferably at most 400 ° C, but more preferably 250 ° C. A single curing step is preferred. The resulting cured film thickness depends on the dilution of the polymer solution and is typically in the range of from 10 to 1000 nm. When measured using a tool at a wavelength of 632 nm, the refractive index of the film is between 1.4 and 1.7. The film preferably has a thermal stability of up to 400 ° C and a minimum outgassing of the volatile components to reduce the adverse effects on subsequent coating or processing in semiconductor fabrication.

1 shows a lithography process: depositing a hard mask on a substrate to be patterned, depositing a photoresist, exposing the photoresist, developing the photoresist, etching the hard mask, and removing the light A resist that etches the pattern of the desired material and removes the hard mask. According to the embodiment shown in the figures, the material is applied to the substrate 10 by means of spin coating. Other coating methods may also be suitable if the application of the material is required. After coating, the material is then cured to create a hard mask 20. A photoresist 30 is then applied to the hard mask and processed (exposed and developed) to produce a pattern of exposed hard masks. The pattern is then transferred to a hard mask by dry or wet etching. The photoresist can be removed prior to etching the substrate through an open pattern created on the hard mask, as is well known to those skilled in the art. Finally, after etching a deep high aspect ratio via on the substrate, the hard mask is removed using a dry or wet cleaning procedure. However, if the technique is sufficient to transfer the pattern, it may be preferable to simultaneously pattern the hard mask material during development of the photoresist. This can be done when the hard mask layer is developed with the photoresist, and this can result in significant time and cost savings when the hard mask does not require a separate pattern transfer step by wet or dry etching.

2 shows a substrate 10 and a photoimageable hard mask 20. Use map The photoimageable hard mask shown in Fig. 2 comprises depositing a hard mask on the substrate to be patterned, exposing the patternable hard mask, developing the soluble portion of the exposed hard mask, and etching the desired material. Pattern and remove the hard cover.

Examples 1 to 3 describe materials prepared and cured in this manner. These materials were subjected to common deep reactive ion etching (DRIE) etching conditions (Table 1). Its etch selectivity to Si is shown in Table 2.

A standard pattern of alumina coating film is formed using a photoresist using a common pattern transfer. The deep D-holes were formed using the same DRIE conditions and the Si protected by the alumina hard mask was not degraded (Figures 3-5).

A better method of creating a pattern on a hard mask is to prepare a hard mask that can be patterned by photolithography. In this case, manufacturing time and cost can be greatly saved. A patterned hard mask (Fig. 2) can be obtained via a technique for a negative tone photoresist, the technique comprising coating a substrate (10), drying, exposing the hard mask (20) via a mask, exposing Post-baking, developing the non-exposed areas and final curing. After etching, the hard mask is removed using a dry or wet cleaning procedure. Similarly, a patterned hard mask can also be obtained via techniques for positive tone photoresists. The use of latent radiation-sensitive catalysts provides the possibility of cross-linking alumina-based hard masks. The latent catalyst decomposes upon exposure to radiation to produce an acid or free radical that causes the functional group to react. The exposed portion is cured due to the condensation reaction catalyzed by the strong acid released by exposure. The curing can also be achieved by other methods, with the proviso that the functional groups present in the composition of the polymer can undergo polymerization initiated by acid or free radicals. As described previously, the use of a precursor 2 or 3 containing a reactive R ² or R ³ substituent such as an alkenyl group, an alkynyl group, an epoxy group, an acrylate group, and an alkyl acrylate group allows the material to be The catalyst activated by exposure to light of the desired wavelength is used in combination to cure via the latter mechanism. In the negative color modulation process, when the illumination passes through the patterned mask, the area through which the light passes to the film will solidify. The non-exposed areas can then be dissolved in the aqueous developer such that the pattern on the mask is transferred to the film. Prior to exposing the film to radiation, a heating step is performed to remove volatile components from the formulation. This temperature is between 50 and 170 ° C, preferably between 70 and 150 ° C, which does not cause premature crosslinking of the resin which may cause the non-exposed areas to be insoluble to the developer. Similarly, after exposure, post-exposure bake is performed to accelerate the reaction initiated by the latent catalyst. For a positive color modulation process, the image is actually reversed compared to the negative color modulation process. Therefore, the exposed region of the positive-tone material is dissolved in the developer.

A patternable material can also be obtained when the precursor 2 carries a reactive functional group that can be initiated by a radiation-sensitive latent catalyst. For those skilled in the art, this and the above provide the possibility of forming a patterned structure when guiding light through the mask and stepper.

To obtain a patternable material, the amount of precursor 2 or 3 containing the reactive R ² or R ³ substituent is important. It has been found that 10% of the reactive precursor 3 is insufficient to produce a patternable material (Example 4). Similarly, it was found that excess or insufficient amount of precursor 2 resulted in no favorable pattern formation or minimal formation of a favorable pattern (Example 9).

In the process of forming deep high aspect ratio through holes, the removal of the alumina hard mask can also be omitted. Therefore, it is expected that the CTE value of the alumina-based material will be connected. The CTE value of the near sputum. The similarity of the CTE values is important in non-sacrificial applications of materials to minimize the mechanical stresses experienced during and after various manufacturing steps (involving high temperatures) or the thermal mismatch experienced in the device.

Alumina-based hard mask films containing groups capable of absorbing light can be used in advanced lithography applications that form narrow line widths. A light absorbing group may be introduced as a substituent of hydrazine (R 3 in the precursor ³ ) or as a ligand coordinated to aluminum (R ² in the precursor ² ). In the lithography application, the ability to control the optical properties of the film, such as refractive index and extinction coefficient, is important. Examples 6-8 describe the synthesis of materials in which the optical constants can be adjusted by controlling the substituents in the alumina-based hard mask and their contents. The optical constant values for the various wavelengths used in lithography applications are shown in Figures 7-9. For those skilled in the art, the refractive index and extinction coefficient can be adjusted by selecting the light absorbing compound and its amount in a given hard mask composition. Thus, the light absorbing portion is not limited to the groups given in the examples and other portions of the wavelengths known to absorb can be used to adjust the optical constants suitable for a particular application.

Based on the above, in one embodiment, the method of the present invention includes the step of patterning the hard mask using lithography and etching. This embodiment comprises a combination of the following steps: - depositing a hard mask material by means of spin, slit coating, spraying, or other suitable method of coating the material in solution; making the hard mask material at the desired temperature Curing; - depositing, patterning, and developing a photoresist on the hard mask to expose a desired area of the hard mask; - transferring the pattern from the mentioned photoresist to a specified exposed area of a given hard mask by means of selective etching; - removing the patterned photoresist using conventional etching techniques as appropriate; and - using The etching process transfers the pattern from the hard mask and photoresist mentioned to a given substrate.

In the final step, an etching process which is highly selective and does not cause damage to the non-exposed areas of the substrate due to improper reaction of the hard mask layer is preferably used.

In one embodiment, the hard mask composition contains at least an Al-O- and -Si-O-resin core with an organic substituent. In another embodiment, the hard mask composition contains at least an Al-O-resin core with an organic substituent.

In one embodiment, the resulting structure can exhibit an etch selectivity between the hard mask and the substrate of at least 500:1. However, it can also vary over a wide range of about 10,000:1.

In one embodiment, the curing of the coating film is carried out on a hot plate at a temperature of from 200 to 400 ° C, preferably from 200 to 300 ° C. In another embodiment, the curing of the coating film is carried out in an oven at a temperature of from 400 to 1000 ° C, preferably from 400 to 650 ° C.

In any of the above embodiments, a developer comprising a dilute tetramethylammonium hydroxide (TMAH) solution or a dilute TMAH solution may be used.

The process of the present invention can be used in embodiments where the purpose is a via structure having a high aspect ratio. Thus, in one embodiment, the process produces a high aspect ratio via structure on a semiconductor substrate, wherein the aspect ratio is at least 5:1 or More preferably 50:1 higher. In another embodiment, the process produces a high aspect ratio via structure on the semiconductor substrate, wherein the via depth is 100 microns, preferably more than 200 microns.

It will be apparent that the present invention can be used in various methods of performing semiconductor lithography, etching, and via formation processes using a protective alumina-based hard mask layer capable of absorbing light used in lithographic processing.

In another embodiment, the invention includes a method of forming a thin film hard mask on a substrate, comprising the steps of: - hydrolyzing the surface of the substrate with a precursor of the first metal oxide by using a hydrolysis catalyst in the presence of a peptizing agent and a solvent The chemical composition obtained by the reaction; - optionally reacting the first metal oxide precursor with a second metal or metalloid oxide precursor; to produce an intermediate oligomer or polymeric material Solution; - performing a solvent exchange process on the intermediate chemical solution as appropriate; - heating the film hard mask at a high temperature to partially or completely remove the solvent crosslinking reaction; and - processing by semiconductor photolithography Film hard cover.

In the method, it will be apparent from the above that the first metal oxide precursor may be selected from the group consisting of aluminum chloride, aluminum alkoxide, aluminum nitrate, aluminum acetate, aluminum acetacetate precursor, and combinations thereof.

In one embodiment, the intermediate oligomer or polymeric film hard mask can be cured at elevated temperatures and can be patterned by lithography using a negative lithography process.

In any of the above embodiments, the R ³ group is preferably a mixture of a phenyl group and a polyaromatic compound. This embodiment achieves predetermined optical properties by lithographic patterning.

More specifically, examples of applications in which materials act as hard masks include:

A. Hard mask compatible with redistribution, wafer bump dielectric or passivation layer. In particular, a hard mask can be applied to a dielectric (organic, hybrid or inorganic) material, typically patterned in a lithography process and subsequently removed using a moderate chemical stripping chemistry without removal or damage. Dielectric film. The stripping selectivity can be adjusted during the polymerization using an organic additive such as acetoacetate (acac).

B. A hard mask containing organic groups that absorb the lithography process wavelength (typically 193 nm to 460 nm). This light attenuating component allows the material to be used in the antireflective coating function simultaneously in combination with photoresist lithographic patterning.

C. A hard mask compatible with a second transfer layer material such as a spin-on-carbon (SOC) polymer. A hard mask can be applied to the SOC polymer to enhance overall stack selectivity. After the vias are patterned, moderate wet chemical removal can be used to remove the stack.

D. Hard masks and etch stopers in the manufacture of dual damascene interconnects. In the dual damascene process, SiCxNy or SiOxNy is used as an etch stop for separating the Cu content. By replacing the conventional etch stop agent with the material, the via height can be reduced, thereby reducing the total Cu line length.

E. Hard mask for micro-electro-mechanical system (MEMS) manufacturing. The material can be patterned into the desired shape using photolithography. The vertical dimension is adjusted by etching the substrate.

In addition to forming deep high aspect ratio structures, potential applications of materials can also be included. The specific example includes:

A. Passivation application in which high mechanical properties are required.

B. Shallow trench isolation for logic devices and memory devices. The material can also be used as a fill material for isolated shallow trenches.

The following non-limiting examples illustrate the invention.

Example 1

Aluminum isopropoxide (15 grams) and THF (52.5 grams) were placed in a round bottom flask equipped with a magnetic stir bar and a reflux condenser. Once the aluminum isopropoxide was dissolved, acetamyl pyruvate (acac, 7.35 grams) was added dropwise. The mixture was stirred at room temperature for 1 hour and then methanol (52.5 g) was slowly added, followed by a mixture of 0.01 M HNO ₃ (5.29 g) and isopropanol (5.29 g). After the addition was completed, the reaction mixture was refluxed for 16 hours by placing the flask in a 100 ° C oil bath. When the reaction mixture was cooled to room temperature, the volatile material was removed under reduced pressure until 35.4 g of mixture remained. 2-butanone (95 grams) was added and the evaporation step was repeated until 33.7 grams of material remained. The resulting solution was then formulated with 2-butanone and methanol to produce a solution which was spin coated onto the substrate. After curing at 200 ° C, a coating film having a refractive index of 1.50 and a thickness of 81 nm was obtained.

Example 2

Repeat above using acac (3.68 grams). The resulting solution was then formulated with 2-butanone and methanol to produce a solution which was spin coated onto the substrate. After curing at 200 ° C, a coating film having a refractive index of 1.44 and a thickness of 108 nm was obtained.

Example 3

Aluminum isopropoxide (3 grams) and ethanol (11.25 grams) were placed in a three-necked round bottom flask equipped with an overhead stirrer and a reflux condenser. The flask was immersed in a 100 ° C oil bath. After 5 minutes, slowly adding deionized water (22.5 g) and 60% HNO ₃ (0.14 g) and the mixture was refluxed for 24 hours. The reaction mixture was further formulated using deionized water and ethanol. The solution was spin-coated on a substrate and cured at 200 ° C to obtain a coating film having a refractive index of 1.50 and a thickness of 93 nm.

Example 4

The preparation of Example 2 was repeated. After removal of the volatiles, 42.5 grams of material having a solids content of 18.1% was obtained. In another reaction, glycidoxypropyl-trimethoxydecane (5 g), acetone (10 g), and 0.01 M HNO ₃ (1.14 g) were stirred at room temperature for 24 hours to give a glycidyloxy group. Hydrolyzate of propyl decane. The aluminum-containing solution (3 g) was mixed with 0.44 g of the glycidoxypropyl decane-based hydrolyzate to obtain a copolymer having an Al:Si molar ratio of 9:1. The homogenous mixture was heated at 60 ° C for 30 minutes. The material was formulated with a photoacid catalyst, coated and exposed via a mask. After development, no pattern was obtained.

Example 5

Repeat the procedure of Example 4. The molar ratio of Al:Si is set to 7.5:2.5. The aluminum containing solution (16.6 grams) was mixed with 7.3 grams of glycidoxypropyl decane based hydrolyzate. The homogenous mixture was heated at 75 ° C for 45 minutes and the resulting solution was formulated with cyclohexanone and a photoacid generator. The solution was spin-coated on a substrate and cured at 200 ° C to produce a coating film having a refractive index of 1.51 and a thickness of 152 nm. The material can be patterned using photolithography (Figure 5).

Table 2 shows the properties of the materials prepared by the following examples and the etch rate results compared to standard photoresists. The etch rate 1 based on the Bosch type and the etch rate 2 based on the low temperature DRIE process.

Example 6

The preparation of Example 2 was repeated. After removal of the volatiles, 263.97 grams of a material containing alumina having a solids content of 19.76% was obtained. In another reaction, acetone (49.76 grams) and phenyltrimethoxydecane (51.76 grams) were placed in a round bottom flask equipped with a Teflon-coated magnetic stir bar and a reflux condenser. Nitric acid (0.01M, 14.10 The gram was added dropwise to the flask and then the reaction mixture was stirred at room temperature for at least one hour. A 10.0 gram alumina solution was placed in a 50 ml round bottom flask equipped with a Teflon-covered magnetic stir bar and a reflux condenser. An alumina mixture containing 10 mol% of a phenyl alkoxy group was obtained by dropwise addition of 0.92 g of a phenyl decyloxy hydrolyzate. The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 10 minutes. Obtain a highly viscous gelatinous material and store at room temperature overnight. Next, n-propoxypropanol (PNP, 15 g) was added and 6 drops of concentrated nitric acid were added while vigorously stirring the mixture. The material was then filtered and spin-coated at 2000 revolutions per minute (rpm) and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.5171 and a thickness of 134 nm.

Example 7

The preparation of Example 6 was repeated. An alumina mixture containing 5 mol% of phenyl alkoxy group was obtained by dropwise addition of 0.43 g of a phenyl alkoxy hydrolyzate. The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 30 minutes. Obtain a highly viscous gelatinous material and store at room temperature overnight. Next, cyclohexanone was added, the material was filtered and spin-coated at 2000 rpm and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.4555 and a thickness of 427 nm.

Example 8

The preparation of Example 6 was repeated. A 5 mol% phenyl decyloxy group was obtained by dropwise addition of 0.20 g of a phenyl decyloxy hydrolyzate and 0.79 g of a phenanthryloxy hydrolyzate prepared in a manner similar to a phenyl decyloxy hydrolyzate. And a mixture of 5 mole % phenanthryloxy alkoxide. The two hydrolyzates were simultaneously added dropwise to the solution containing alumina. In the room The mixture was stirred at room temperature for 5 minutes and then placed in a 75 ° C oil bath for 20 minutes. Obtain a highly viscous translucent gelatinous material and store at room temperature overnight. Next, n-propoxypropanol (PNP, 15 g) was added and 6 drops of concentrated nitric acid were added while vigorously stirring the mixture. The material was then filtered and spin-coated at 2000 rpm and cured at 200 ° C for 5 minutes to obtain a film having a refractive index of 1.5456 and a thickness of 194 nm.

Example 9

Aluminum isopropoxide (5 grams) and isopropyl alcohol (IPA) (15 grams) were placed in a round bottom flask equipped with a magnetic stir bar and covered with argon. Once the aluminum isopropoxide was dissolved, ethyl benzamidineacetate (1.95 g) was added dropwise. The mixture was stirred at room temperature for 5 minutes, followed by the addition of hydrochloric acid (10M, 0.01 g) and water (0.38 g). After the addition was completed, the reaction mixture was stirred at room temperature for 16 hours. A solution having a solids content of 31% was then formulated with Irgacure 819 (5 wt%) and filtered (0.1 micron), followed by spin coating. The coated material can be patterned by photolithography to produce a positive tone image.

10‧‧‧Substrate

20‧‧‧hard cover

30‧‧‧ photoresist

Figure 1 shows in a simplified manner a process for applying a hard mask in a lithography application.

Figure 2 shows a similar depiction of coating a photoimageable alumina-based hard mask material in a lithography application.

3 shows a side view of a deep via formed on a crucible using the polymer of Example 1 as a hard mask in a packaged DRIE etch.

4 shows a side view of a deep via hole formed on a crucible using the polymer of Example 1 as a hard mask in a low temperature DRIE etch (AR=7).

Figure 5 shows a deep via formed on the crucible using the polymer of Example 3.

Figure 6 shows the pattern obtained by photolithographic processing of the material prepared in Example 5; the resolution of the pattern: 5 microns, 4 microns, 3 microns, 2 microns and 1 micron.

Figure 7 shows the optical constants (refractive index and extinction coefficient) of a coating film based on Al _x O _y copolymerized with 10% phenyl decane as a function of wavelength.

Figure 8 is a graph showing the optical constants (refractive index and extinction coefficient) of a coating film based on Al _x O _y copolymerized with 5% phenyl decane as a function of wavelength.

Figure 9 shows the optical constants (refractive index and extinction coefficient) of a coating film based on Al _x O _y copolymerized with 5% phenyl decane and 5% phenanthrene, as a function of wavelength.

10‧‧‧Substrate

20‧‧‧hard cover

30‧‧‧ photoresist

Claims (28)

A method of forming a protective hard mask layer on a substrate in a semiconductor etching process, comprising the step of applying a solution or colloidal dispersion of an alumina polymer to the substrate by solution deposition, the solution Or the dispersion is obtained by hydrolyzing and condensing a monomer of at least one alumina precursor in a solvent or solvent mixture in the presence of water and a catalyst. The method of claim 1, wherein the solution or dispersion is subjected to acid or base catalyzed hydrolysis of the monomer of the at least one alumina precursor in a solvent or solvent combination in the presence of water. And the condensation reaction is carried out to produce a solution or colloidal dispersion of the alumina polymer. The method of claim 1, wherein a plurality of alumina precursors are used to make a solution or colloidal dispersion of the alumina polymer. The method of claim 1, wherein the one or four alumina precursors are copolymerized with the decane precursor in a solvent or solvent combination to produce a solution or colloidal state of the cerium oxide containing the alumina polymer. Dispersions. The method of claim 1, wherein the alumina precursor comprises a hydrolyzable functional group in an amount of 1 to 3 molar equivalents per hydrolyzed functional group to produce a polymeric material capable of being coated on the substrate. Solution or dispersion. The method of claim 1, wherein the alumina precursor comprises a hydrolyzable functional group in an amount of from 5 to 10 mole equivalents per hydrolyzed functional group to produce a colloidal state capable of being coated on the substrate A solution or dispersion of a polycationic aluminum material. The method of claim 5, wherein the hydrolyzable functional group is selected from the group consisting of the formula OR ¹ wherein R ¹ is selected from the group consisting of a linear alkyl group, a branched alkyl group, and a ring. An alkyl group as well as an aryl group which may be further substituted with a halo, alkoxy, cyano, amine, ester or carbonyl functional group. The method of claim 1, wherein the alumina precursor is selected from the group consisting of a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, a β-diketone, an ester or a β-ketoester. The reagent is peptized, and a C _1-12 alkyl group of a halogen, an unsaturated, and an aromatic functional group may be present to produce a stable solution or dispersion of a polymeric material that can be applied to the substrate. The method of claim 1, wherein the alumina precursor has the general formula AlX _n (OR ¹ ) _3-n wherein R ¹ is independently hydrogen, a linear alkyl group, a branched alkyl group, Select from the group of cyclic alkyl groups and aryl groups; X is independently selected from the group consisting of a chloro group, a bromo group, an iodine group, an ester group, a thiol group, a sulfate group, a thio group, and a nitro group; n is An integer between 0 and 3. The method of claim 1, wherein the alumina precursor has the formula (R ² ) _m AlX _n (OR ¹ ) _2-n wherein R ¹ is independently a linear alkyl group, a branched chain Selected from the group of alkyl, cyclic alkyl and aryl; R ² is independently selected from the group consisting of carboxylic acids, α-hydroxycarboxylic acids, carboxylates, β-diketones, esters and β-ketoesters; X is independently selected from the group consisting of a chloro group, a bromo group, an iodine group, an ester group, a thiol group, a sulfate group, a thio group, and a nitro group; and m is an integer between 0 and 2; n is an integer determined by 3-m. The method of claim 1, wherein the solution or dispersion is a monomer of at least one alumina precursor and a cerium oxide precursor in a solvent or solvent mixture in the presence of water and a catalyst. Hydrolyzed and condensed and obtained, wherein the ceria precursor has the formula (R ³ ) _k -Si-X _4-k wherein R ³ is independently a linear alkyl group, a branched alkyl group, a cyclic alkane Base, alkenyl (linear, cyclic, and branched), alkynyl, epoxy, acrylate, alkyl acrylate, heterocyclic, heteroaromatic, aromatic (from 1-6 Ring composition), alkyl aromatic group (consisting of 1-6 rings), cyanoalkyl group, isocyanatoalkyl group, aminoalkyl group, sulfanyl group, alkyl urethane group, alkyl urea And a group selected from the group consisting of an alkoxy group, a decyloxy group, a hydroxyl group, a hydrogen group, and a chloro-functional group, at least one R ³ being a group in the precursor which acts as a functional group reactive when a latent photoactive catalyst is activated; Independently selected from the group consisting of hydroxyl, alkoxy, sulfhydryl, chloro, bromo, iodo and alkylamine; and n is between 0 and 3 Integer. The method of claim 1, comprising forming the hard mask layer of the formula consisting of the following repeating units on the substrate: -[Al-O _1.5 ] _a -[(R ² ) _m -Al-O-] _b -[(R ³ ) _k -Si-O _2/3 ] _c - wherein R ² is independently from a carboxylic acid, an α-hydroxycarboxylic acid, a carboxylate, a β-diketone, Selected from the group of esters and β-ketoesters; R ³ is independently from linear alkyl, branched alkyl, cyclic alkyl, alkenyl (linear, cyclic, and branched), alkynyl, epoxy Base, acrylate group, alkyl acrylate group, heterocyclic group, heteroaromatic group, aromatic group (consisting of 1-6 rings), alkyl aromatic group (composed of 1-6 rings), cyanide Groups of alkyl, isocyanatoalkyl, aminoalkyl, sulfanyl, alkyl urethane, alkyl urea, alkoxy, decyloxy, hydroxy, hydrogen, and chloro-functional groups It is selected that at least one R ³ is a group in the precursor which functions as a reactive group upon activation of the latent photoactive catalyst, and a, b and c are numerical values. The method of claim 1, wherein the hard mask is patterned on the substrate by using a lithography and an etching step by means of spin coating, slit coating, spraying or Other methods suitable for coating the material in solution state deposit a hard mask material; curing the hard mask material at a desired temperature; depositing, patterning, and developing the photoresist on the hard mask Exposing a desired area of the hard mask; Transferring the pattern from the mentioned photoresist to a designated exposed area of the predetermined hard mask by means of selective etching; removing the patterned photoresist using an etching technique; and using an etching process The pattern is transferred from the hard mask and photoresist mentioned to the predetermined substrate. The method of claim 13, wherein the curing of the hard mask material is performed on a hot plate at a temperature of 200 to 400 °C. The method of claim 13, wherein the curing of the hard mask material is carried out in a furnace at a temperature of from 400 to 1000 °C. The method of claim 13, wherein the step of creating a high aspect ratio via structure on the semiconductor substrate, wherein the aspect ratio is at least 5:1. The method of claim 13, wherein the step of creating a high aspect ratio via structure on the semiconductor substrate, wherein the via depth is 100 microns. The method of claim 13, wherein the etch selectivity between the hard mask and the substrate of the resulting structure is at least 500:1. The method of claim 13, wherein the developer is a dilute tetramethylammonium hydroxide (TMAH) solution. The method of claim 13, wherein the hard mask material comprises at least an Al-O- and a -Si-O-resin core having an organic substituent. The method of claim 13, wherein the hard mask material comprises at least an Al-O-resin core having an organic substituent. A method of performing semiconductor lithography, etching, and via forming processes using a protective alumina-based hard mask layer capable of absorbing light used in lithography processing, the process including, for example, claim 1 to 21 The steps of any of the items. The method of claim 22, wherein the hard mask material is composed of a material of the following structure: -[Al-O _1.5 ] _a -[(R ² ) _m -Al-O-] _b -[ (R ³ ) _k -Si-O _2/3 ] _c - wherein a, b and c are numerical values; and R ² is an organic acid having an organic functional group having light of a wavelength capable of absorbing the light lithography of the material a peptizer selected from the group consisting of β-diketone or β-diketone ester, and R ³ is independently a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group (linear, cyclic) And a branched chain), an alkynyl group, an epoxy group, an acrylate group, an alkyl acrylate group, a heterocyclic group, a heteroaromatic group, an aromatic group (consisting of 1 to 6 rings), an alkyl aromatic group ( Composition of 1-6 rings), cyanoalkyl, isocyanatoalkyl, aminoalkyl, sulfanyl, alkylcarbamate, alkylurea, alkoxy, decyloxy, hydroxy Among the groups of hydrogen, chloro-functional groups, at least one R ³ is a group in the precursor which acts as a functional group reactive when the latent photoactive catalyst is activated. The method of claim 23, wherein R ³ is an organic functional group capable of absorbing light of a wavelength used in photolithographic processing of the material. The method of claim 22, wherein the R ³ group is a mixture of a phenyl group and a polyaromatic compound, which is suitable as an antireflection coating film by lithographic patterning to obtain predetermined optical properties. A method of forming a thin film hard mask on a substrate, comprising the steps of: reacting a surface of the substrate with a chemical composition obtained by hydrolyzing a first metal oxide precursor with a hydrolysis catalyst in the presence of a peptizing agent and a solvent; Cooperating the first metal oxide precursor with a second metal or metalloid oxide precursor to produce a solution of an intermediate oligomer or polymeric material; performing a solvent exchange process on the intermediate chemical solution; The film hard mask is heated to perform a cross-linking reaction in which the solvent is partially or completely removed; and the film hard mask is processed according to a semiconductor lithography method. The method of claim 26, wherein the first metal oxide precursor is aluminum chloride, aluminum alkoxide, aluminum nitrate, aluminum acetate, aluminum acetacetate precursor or a combination thereof. The method of claim 26, wherein the heating of the film hard mask at a high temperature is patterned by a lithography method according to a negative lithography process.