TW468209B - Layered resist system using tunable amorphous carbon film as a bottom layer and methods of fabrication thereof - Google Patents

Abstract

Disclosed is vapor deposited thick are layer and method of preparing single and tunable thick bottom layer coatings based on amorphous carbon films. These films can be hydrogenated fluorinated nitrogenated carbon films. Such films have the index of refraction and the extinction coefficient tunable from about 1.4 to about 2.1 and from about 0.1 to about 0.6 respectively at UV and DUV wavelenghts, in particular 365, 248 and 193 nm. This makes the films extremely useful to be used as thick bottom layers in a bilayer resist system. Moreover, the films produced by the present invention can be deposited over device topography with high conformality, and they are etchable by oxygen and/or fluorine ion etch process. Because of these unique properties, these films can be used to form a single or tunable thick bottom layer at UV and DUV wavelenghts to produce practically zero reflections at the resist/bottom layer interface. This greatly improves performances of semiconductors chips.

Description

Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ6 B2〇9 Α7,' 1. —- Β7 V. Description of the invention (, y " ~~ r ~ 明 L Ming Fan Yuan, the invention of this invention is about The structure of the body circuit is particularly related to the use of an amorphous carbon film with an adjustable thickness to coat you for a two-layer photoresist system and a manufacturing method therefor. BACKGROUND OF THE INVENTION Logic and memory chips Reduced element size to 0.25 μm and more. The single-layer photoresist used cannot be used in conventional exposure tools. Ultraviolet (UV) and deep ultraviolet (DUV) wavelength substrate reflection is not conducive to standing wave effect and light The generation of resistance notches strictly limits the tolerance of the critical dimension (CD). The notches are caused by the shape of the substrate and the uneven reflectance of the substrate, which results in a change in the area of the exposed energy on the photoresist. The standing wave is Thin interference or periodic changes in light intensity when passing through the thickness of the photoresist. These light changes are introduced because the photoresist is flattened to show different thicknesses when passing through the shape below. Thin interference is in the CD control of the single-layer photoresist process. Decisive angle Therefore, a small change in the optical phase will cause a large change in the effective exposure dose. Line width control is one of the most important provisions in useful lithography processes-the typical standard is that the print line width must be at the target value 10%. There are multiple process variables that can change the line width. The simulation in Figure 12 shows how the photoresistance line width changes with the exposure energy. The line prints about 1 OmJ / cm2 of exposure energy, which is close to 0.25 microns. Target size, underexposure at 8.5mJ / cm2 will print 0.14 micron lines, and overexposure at 12.5mJ / cm2 will print 0.14 micron lines. Β prints the desired 0.25 micron line to 10% standard The only way among them is to carefully control the exposure energy. Unfortunately, there are many process factors that can affect the exposure energy in photoresistors. This kind of storm -4- This paper is in accordance with the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) ( (Please read the notes on the back before filling this page) Packing. -1Τ 82 〇9 Α7 Β7 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The Invention Note (2-) The most important special electric power that changes is due to Film interference effect In accordance with "Optimization of optical properties of resist processes" (T. Brunner, SPIE Proceedings Vol. 1466, p.297, 1991), thin films such as silicon nitride or silicon oxide have been used in semiconductor manufacturing. There are some changes in its thickness that cause changes in the exposure energy into the photoresist. Let us consider how things change when the photoresist is above the variable thickness of silicon oxide as shown in the simulation. Figure 13 shows the crystal The total reflectance of the circle is a function of the thickness of the oxide (layer # 1). Obvious sine wave changes can be seen, with a Sinus reflection of 50 and a minimum reflection of about 20%. Figure 14 shows the calculated photoresistor line width 'as a function of oxide and illustrates that the line width is greatly affected by small changes in thickness. The comparison of Figures 13 and 14 shows that the line width is small (overexposed) when the photoresist reflection is small, and the line width is large (underexposed) when the photoresist reflection is large. The following mechanism means that the exposure energy in the photoresist caused by the interference of the thin film changes with the thickness of the oxide. Retroreflective coating or arc has been used to reduce this effect, and we are going to consider an example with our carbon ARC. Figure 15 shows a thin film stack with photoresist on top of 'ARC layer # 1, oxide layer # 2, and Silicon substrate. Figure 16 shows photoresist reflection as a function of oxide thickness. The appearance of ARC has produced approximately 8% reflection * almost independent of the oxide thickness to indicate that the exposure energy does not change the oxide thickness in many changes. ^ As expected, the line width vs. oxide thickness curve in Figure 17 is almost It is flat, and the entire range of data can easily meet the + -10% line width control standard. Modern semiconductor processes sometimes have many thin films with varying thicknesses, and photoresist films themselves can have varying thicknesses. The ARC layer can be roughly used to reduce the application of the Chinese Standard (CNS) M specification for the 5-Thai paper scale (21 × 2 ~ 7 public epidemic disease) ^ --- 1J --- 7-- ', installed-(please first (Read the notes on the back of the 53 and then fill out this page)

'ST,% 0 b 3 Amendment / Correction / Supplement 4 6 8 Next to Z 8〒113920 Application Patent A7 Chinese Manual Correction Page (July 90) B7 V. Description of the Invention (3) Process Noon Line width is dependent on the thickness of multiple layers. The CARC in this patent application is a method with many advantages, as detailed below. In order to overcome these problems, a multilayer system is disclosed. In this design, a first thick bottom polymer layer with UV-DUV absorption is spin-coated on the substrate. This layer has two effects: the planarization of the bottom layer of the structure to minimize TFI and the wetness of the substrate skin (notch). The second thin silicon contains a photoresist layer spin-coated on it. This thin layer is used as a high-resolution image layer, and as a transmission pattern layer after photoresist development, it is used for cutting with oxygen-supplying reactive ions. Because under the protection of its dream essence, the bottom layer will not be attacked by the developer, and the photoresist upper layer will not be etched by the oxygen plasma. Details of this process can be found in Example 5. An extensive discussion of multilayer photoresist technology can be found in the following literature: "pollyerie silicon-containing resist materials", RD Miller and G. M. Consumer Promoters, Central Prototype Bureau, Ministry of Economic Affairs Printed (Please read the notes on the back before filling in this page)

Wallraff, Advanced Materials for Optics and Electronics, Vol. 4, 95-127 (1994). The bottom layer currently used is novolac photoresist, which can be found in the following documents: " Bilayer resist approach for 193 nm lithography ", Schaedely et al.s Proc. SPIE-Int. Soc. Opt. Eng. (USA) Vol_2724 1996 , p334-54. The main problems associated with this spin-coated polymer material are good submicron structure consistency, poor optical tunability, and chemical interactions at the interface with image photoresist, which can produce a critical dimension (CD). Variety. If a thick single-layer photoresist is used instead of a double layer, a mechanical breakdown of the photoresist pattern will occur, as described in the following document "Characterization of the resist pattern collapse in a chemically amplified resist", Cha-Won Koh, Cheoul -Kyu Bok, Ki-Ho Baik, Interface 1996 -6- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) d682〇9 A? B7 Description of the Invention (4), Proc, p295-302, S. Diego Ca. 1996. An object of the present invention is to provide an improved photoresist. Another object of the present invention is to provide an improved photoresist formed from a plurality of layers. Another object of the present invention is to provide a photoresist having a plurality of layers, wherein the bottom layer is a thick adjustable layer. The purpose of the present invention is to propose the formation of a bottom planarization layer by vapor deposition. When used in a two-layer and three-layer photoresist system, the vapor-deposited film has greatly increased optical purity compared to a spin-coated polymer. With adjustability. Another object of the present invention is to provide a method for depositing a C: H film by vapor deposition, which has the required optical properties to facilitate the formation of a DUV (365, 248, 193 nm in a two-layer / three-layer system). ) The bottom layer. These films have wide optical tunability, that is, n and k can be changed by changing the process conditions. These films can be easily patterned in the opposite direction and removed by an oxygen plasma. This method can be easily extended to the manufacturing tools currently used in the semiconductor industry. Another object of the present invention is to perform deposition by depositing in an Ar / Carbonium compound / Helium / Fluorine compound / Nitrogen / Oxygen mixture, preferably the hydrocarbon is cyclohexane or acetylene, and the carbon The fluorine compound is benzene hexafluoride. A higher refractive index can be obtained by restricting or removing the hexafluorobenzene (HFB) flow in the plasma chamber. By increasing the HFB flow and restricting or removing the hydrocarbon gas flow, A lower refractive index can be obtained. A high extinction coefficient k can be obtained by depositing a film by using a high cathode bias voltage, and a low k value can be obtained by reducing the bias voltage. Use appropriate nitrogen and / or oxygen flow to achieve finer optical tunability, use hydrogen to adjust optical properties and film durability (____ + This paper size applies to China National Standard (CNS) A4 ^ grid (210X297 mm) ） I --- J --- ^ --- '·, > Equipment 丨-(Please read the notes on the back before filling this page) -Order II ·: I · • II-46 8209 Central Standard of the Ministry of Economic Affairs A7 printed by the Bureau Cooperative Consumer Cooperative __________ B7 V. Description of the Invention (5) Another object of the present invention is to provide a method for depositing an amorphous carbon film by using vapor deposition as a bottom layer in a double-layer photoresist system. Among them, the optical properties have been optimized to minimize the reflections that occur on the substrate and the photoresist / bottom interface. This substrate is then used as a thick planar anti-reflection coating (arc), which will also make the film Interference is minimized. Process gas chemistry and process parameters are usually uniquely adjusted to achieve the desired optical properties. Another object of the present invention is to provide a method for vapor deposition of a thick arc layer, in which refraction Index η and disappearance coefficient k Changing to form an improved anti-reflector "will show an example where the ARC layer is divided into three different layers with different optical properties. We show that this layer has very low reflections and has a high tolerance for process changes. Our The deposition technique is also applicable to a layer in which the optical properties are graded as the film depth changes. This can be referred to as follows: Tanaka et a. In SPIE Vol. 2726, P. 573 (1 996). More importantly If n and k of the thin ARC layer are technically perfectly matched with the adjacent layers, non-reflection will greatly improve CD control. All the teachings of the previous case mentioned in this article are here for reference. One of the broad features of the invention is a multilayer photoresist system and its manufacturing method. [Beta] One of the more specific features of the present invention is the manufacture of a multilayer photoresist system and aC: X: H film with adjustable optical properties by vapor deposition Method, where χ is fluorine, nitrogen and oxygen. Another more specific feature of the method and structure according to the present invention is to deposit-hydrogenated carbon by vapor deposition from a carbon < compound / fluorocarbon / hydrogen plasma, Xi plasma has Optically small amount of nitrogen and / or oxygen, if each is deposited ~ This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling this page) : tr i d6B2〇9 A7 B7 Printed by the Ministry of Economic Affairs and the Central Bureau of Standards, printed by the Masonry Consumer Cooperative, V. Description of the invention (s > seem. The film produced here has a refractive index hit and disappear ^ coefficient, which can be individually adjusted to 365,248, 193 nm, making it particularly suitable for thick flat anti-reflective coatings. In addition, the film formed by the present invention can be uniformly deposited on the shape and used as a bottom layer in a multilayer photoresist system, and can be easily patterned and removed from the oxygen and / or fluorine reactive ion etching process, so it is convenient for pattern supply. For wafer manufacturing "Another and more specific feature of the method and structure according to the present invention is to deposit an amorphous carbon film by vapor deposition, which includes the following steps: mixing hydrocarbons, fluorocarbons, hydrogen, and also adding Providing a small amount of oxygen and / or nitrogen; providing a reactor chamber including a cathode and a substrate; and introducing the above-mentioned gas mixture into the chamber; and applying an rf bias voltage to the cathode to initiate a plasma and passing gas Phase deposition to deposit an aC: × Ή film on the substrate. Another and more specific feature of the method and structure according to the present invention is the deposition of an amorphous carbon film using a gaseous mixture comprising: benzene hexafluoride, hydrogen, cyclohexylene; and acetylene, which may or need not be in He or Dilute in Ar to deposit a film reactively by vapor deposition. By using this method, the refractive index n and the disappearance coefficient k can be optically adjusted separately at UV or DUV wavelengths. In particular, the UV and DUV indices and the extinction coefficient k of the refraction η can be adjusted from about 1,40 to about 2.1, and from about 0.1 to about 0.6 at 365, 248, and 193 nm, respectively. These films therefore meet the requirements for use as a thick, planar substrate in a two-layer photoresist system. Brief Description of the Drawings Fig. 1 is a schematic view of a vapor deposition apparatus used for carrying out the present invention. The graph in Figure 2 shows the definition of the swing ratioa. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (谙 Read the precautions on the back before writing this page)

468209 Printed by A7 B7, Central Standard of the Ministry of Economic Affairs, Bianzhengong Cooperative Co., Ltd. 5. Description of the invention (7)-Figure 3A, 3B shows the reflection contours (constants) in the thickness functions of η and k (above) and k and Si02 at 3 00 nm. The profile of reflection r2 Figure 4A '4B shows the n and k (top) and k and SiO2 thickness functions at 500 nm bottom (the profile of constant reflection r2) Figure 5A' 5B shows the n and k (top) at 700 nm bottom And the reflection profile in the thickness function of k and SiO2 (the profile of constant reflection R2) Figure 6A shows the reflection profile (the profile of constant reflection R2) in the η and k (upper) function of the 500 nm tunable bottom layer, while Figure 6B is a multilayer Schematic diagram of the resistive structure. Figure 7A (above), the measured reflection and calculated transmittance of a carbon layer of approximately 500 nm thick as described in Example 4, and 7B (below) shows the corresponding calculated n and k values. Figure 8A (above) Example The measured reflection and calculated transmittance of the carbon layer with a thickness of about 100 nm described in 4, and 8B (below) show the corresponding calculated η and k values. Figure 9 shows the process flow of a photoresist double-layer system. Figure 10A, 1 0B shows a SEM image of a photoresist line manufactured using a double-layer photoresist process. Table of optical properties of a sample according to the present invention. Figure 12 simulates how the photoresistor line width changes with exposure energy. Figure 13 shows the total reflectance of the wafer as a function of oxide (layer # 1) thickness. Figure 14 display meter. Calculated photoresistor line width as a function of oxide thickness, and shows that small changes in thickness can greatly affect line width. Figure 15 shows a thin film stack, which is arranged in the order of photoresistors, ARC layer # 1 , Oxidation layer # 2, Mengdi Village. -10- The paper ^ degree applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ --- ^ J --- ^-Λ / pack-(Please (Read the notes on the back before filling out this page)

* 1T _ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ 82 Ο 9 Α7 _____ Β7_ ___ V. Description of the invention (8 > Figure 16 shows photoresistance reflection as a function of oxide thickness. Figure 17 shows line width And oxide thickness curve. Detailed description The present invention relates to a structure and a method for manufacturing the same. The structure is produced from a membrane hydrogen compound and / or a fluorocarbon (fluorocarbon) plasma by a vapor deposition method, and a high-quality hydrogenated carbon film is formed. When used as a thick planarized optically adjustable bottom arc in multiple layers, it is best to use a two-layer / three-layer photoresist system. The film produced by the present invention has an adjustable refractive index and extinction coefficient, which can be selectively selected along the film thickness. The gradient is matched to the optical properties of the substrate and the photoresist. The optical properties of UV and DUV and the lithographic characteristics of the film produced by the present invention are far superior to other polymer films such as diazoamine nequinic acid novolac type photoresist. Obtained, this can be referred to "R D.

Miller and G.M.Wallraff, Advanced Materials for Optics and Electronics, Vol. 4,95-127 (1994) ". Therefore, the silicon substrate coated with the thick planarized amorphous carbon film of the present invention can greatly reduce film interference of UV and DUV wavelengths and substrate reflectivity, which can then improve CD control. Fig. 1 is a pattern of a PECVD (plasma enhanced chemical vapor deposition) deposition apparatus 8 which can be used to deposit the amorphous carbon film of the present invention. The device includes a reaction chamber 10 'having a throttle valve 11 which can separate the reaction chamber 10 from a vacuum pump (not shown). A cathode 19 is mounted on the reaction chamber 10 and separated by a dielectric isolation layer. The cathode 19 is provided with a photoresistive heater 17, and the substrate 15 is fixed to the inner end of the cathode 19. It is intended that the cathode be electrically connected to the RF source 14, which can be adjusted, and that a matching box 13 can be used to match the photoresistance between the cathode 19 and the RF source 14. The circuit is grounded by providing a plate electrode connected to the reaction chamber 10. -11-This paper rule New Zealand national standard (CNS) Α4 size (210X297 male thin) (Please read the note on the back ¥? Then fill out this page) Binding. Order 46 82 〇9 A7 B7 Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau. 5. Description of the invention (9) The reactor 10 also contains ducts 20, 21, 22, 23, 24, 25 for introducing various gas materials into the chamber 10 through the spray head 12, such as hydrocarbons. The gas and pre-mixed hydrocarbon gas mixture will be introduced into the reactor chamber via conduits 25 and 26, respectively. 10β carbon fluoride gas and hydrogen gas will be introduced through conduits 21 and 20, respectively. The duct 23 ′ 22 is introduced into the chamber 10 ′ and the Ar for cleaning the substrate is introduced through the duct 24. The hydrocarbon gas used in the present invention may be any kind of hydrocarbon 'which first vaporizes and then forms a plasma under the reaction conditions used in the present invention. The term% i hydrogen compound refers to some compounds whose composition contains only carbon and hydrogen atoms. According to an embodiment of the present invention, the process may use saturated or unsaturated compounds. A saturated hydrocarbon is defined as a compound whose atoms contain only single bonds, and an unsaturated compound is a compound whose atoms contain carbons with double or triple bonds. It is a particularly preferred embodiment of the present invention, that is, the preferred reaction hydrocarbons and fluorocarbons for forming an amorphous carbon film are cyclohexane and hexafluorobenzene (HFB). Dilute in inert gas. It should be understood that a mixture of hydrocarbon gases such as cyclohexane / acetylene / methane is intended to be used herein as a reactive hydrocarbon gas of the present invention. The gas used in the present invention has a purity of greater than about 95.5%. In the preferred embodiment, the 'gas has a purity ranging from about 98.5 to about 99.99%, and most preferably, the gas has a purity of greater than 99.9%. Pass under different flow controllers with sufficient flow to introduce hydrocarbons' fluorocarbons, hydrogen, helium, and argon into the reaction chamber to provide Ar, hydrogen from about 1 mTorr to 1000 Mtorr ， Hydrocarbons, -12- This paper size applies to the Chinese national standard (CN'S M4 specification (2! 0χ 297 mm > I --- ^-; ---- 71 government-- (% 先 闲Read the notes on the back # 嗔 写 本 耳 j-丁. • -0 46 82 〇9 A7 B7 V. Description of the invention (10) '(Please read the notes on the back before filling this page) Total of fluorocarbons and helium Pressure, in order to provide the most effective amorphous carbon film, the pressure of Ar, gas' hydrocarbons, and helium mixture is preferably about ˜500 Mton. The above conditions can also be achieved by combining Ar, hydrogen, benzene hexafluoride, Hydrocarbon and helium are premixed in one or two or three gas cylinders and combined in any of the possible ways to provide the desired gas concentration. It is better to 'Ar, hydrogen' via different flow controllers The fluorocarbon and hydrocarbon gas are introduced into the reaction chamber. The amorphous carbon film of the present invention can be coated with Suitable substrates for cloth include the following materials such as plastic, metal, various glasses, magnetic heads, electronic wafers, electronic circuit boards, semiconductor devices, etc. The substrate can be coated in any shape or size, and it is assumed that the substrate can be placed in the reaction chamber. Device. Therefore, the present invention can be used with objects of any size, regular or irregular shapes. Preferably, the substrate is a silicon substrate used in the manufacture of semiconductor devices. The β substrate is installed in the reaction chamber of the reactor device. The reaction chamber is then fixed and evacuated until a pressure reading range of about 1x10 to about 1x10. 7 Torr is reached. As described above, when the reaction chamber is evacuated to reach the desired pressure range, then the The substrate is heated to a temperature of from 25 to 400 ° C. Optimally, the substrate is heated at a certain temperature of about 50 to about 200 ° C during the entire deposition process. Consumption by employees of the Central Standardization Bureau of the Ministry of Economic Affairs The substrate material used for printing by the cooperative before the deposition of the amorphous carbon film may or may not be affected by the rf splash cleaning of the rf cathode used in the reaction chamber, and the appropriate cleaning technique used in the present invention Including rf plasmas with hydrogen, argon, oxygen, nitrogen, or mixtures of these, which can be performed individually or in an appropriate sequential combination. After completing the desired pumping force reduction, the premixed gas is about 1 to 100. The flow rate of seem is introduced into the reaction declaration. Preferably, the flow rate of the reaction gas is from the paper scale of the financial institution (CNS… Specifications {21GX297 公 楚) ~~ '46 8209 Central Ministry of Economic Affairs Printed by the Consumer Cooperative A7 B7 V. Description of the Invention (η) — 1 to 100 seem 'and the gas flow rate is from 1 to 100 seem. Optimally, the cyclohexane gas flow rate is about 5 seem. The gas was introduced into the reaction chamber with a dust force of about 5 to 200 mTorr. Another preferred feature of the invention is the introduction of the premix at a pressure of about 100 mTorr. An rf bias voltage is applied to the substrate mounted on the cathode during deposition, and the cathode d C self-bias voltage ranges from −10 to −100 volts throughout the carbon deposition process. Self-bias pressure can be obtained by applying rf power to the cathode, and RF matching can be obtained by using a matching box. Optimally, the substrate rf bias pressure was maintained at -300 volts throughout the experiment. More preferably, the power density applied to the substrate is from 0.005 to 5 W / cm2. Most preferably, the power density used in the present invention is maintained at about 0.62 W / cm2 throughout the deposition process. The rate of the amorphous carbon film deposited on the substrate is such that a substantially continuous film coating can be obtained on the substrate. In particular, by using the above-mentioned operating parameters, the amorphous carbon film can be applied at about 20 to 4000 A / The rate of separation is deposited in the substrate. Optimally, the deposition rate of the amorphous carbon film in the substrate is a rate of about 160 A / min. According to the present invention, the thickness of the amorphous carbon film deposited on the substrate is from 1000 to 5000. A. Preferably, the thickness of the amorphous carbon film is from 3,000 to 7000 a (a Angstrom). It should be noted that the optical constant can be changed by changing the process parameters such as bias pressure, gas flow and pressure. Here, the optical constant of the film is defined as the refractive index η and the disappearance coefficient k. It is therefore possible to produce a substrate with a defined optical constant by diluting cyclohexane or acetylene only in αγ or He, or by changing cyclohexane with a mixture of HFB / hydrogen (Table). In the application of the double-layer photoresist system prepared by the present invention, the 14-wood paper money · size of the underlying amorphous carbon film is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male thin ----- J ------ -Equipment-(Please read the notes on the back before filling in this page), ιτ JJ. 468209 Α7 Β7 Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperation. Fan circles of approximately k = Gl to k = G.6 and n = i.4G to m have wavelengths of 365, 248, and 193 nm. Mainly, the amorphous carbon film formed by the present invention can be regarded as a thick planarization Ideal anti-reflective coating for UV (365 nm) and DUV (248, 193 nm) applications in two-layer photoresist systems. Compared to spin-coated polymers, ARC is a deposition that can be caused by quenching. And greatly improve the optical purity and tunability and integration, thus strengthening the line width control and performance of integrated circuits. Known effective exposure dose in optical lithography The film changes periodically with the thickness of the photoresist. The swing ratio s is defined as the partial exposure change between the maximum interference thickness and the minimum interference thickness. Es is a basic measurement of the quality of a special photoresist process. By reducing the swing ratio, Nearly 0, the photoresistance process can tolerate optical phase changes caused by the uneven thickness of the photoresist and the deposited film. The swing ratio can be calculated using the following formula: S = 4 (R1R2) ° -5e-aD ⑴ where K is the reflectivity of the photoresist air interface, h is the reflectance of the upper photoresistance / ARc interface, "is the absorption coefficient of the photoresistance D is the thickness of the photoresist. In the present invention, we mainly use the best time to use The two-layer photoresist process at the bottom layer is reduced & to reduce the swing ratio D. Figure 2 explains the significance of the above parameters. Generally, the two-layer photoresist system can be modeled to find the bottom layer optical parameters (η and k) and Optimal thickness. In order to achieve this, the optical constants of the entire film structure need to be known to calculate the reduction in wobble ratio. Usually the ARC thickness d varies between 3000 and 7000 A depending on the film absorption, and the disappearance coefficient k can be Between 〇.U to 0.5 The change is more general. 2-15- This paper size is applicable to the Chinese National Standard Flying CNS) M specification (210X 297 Gongchu) " ------ [--- τ --— (Please read the (Please fill in this page again)

.1T Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 6 _ 継 正 号 贴 | Chinese Manual Correction Page (July 90) 37 V. Description of the Invention (13) When the value of k is reduced by 10X swing ratio At DUV it is between 0.1 and 0.3. The refractive index η varies between 1.4 and 2.1, and more generally, the value of η at DUV is between 1.65 and 1 _90. The following examples are in the scope of the steps, because these examples are for illustration purposes only. Therefore, the invention should not be limited by this. Example 1 The following example illustrates the calculations required to obtain the optimal bottom layer parameters of a two-layer system. The parameters have been optimized to reduce reflections from the photoresist / bottom interface. The calculation is based on the following algorithm, which uses the Fissler coefficient, which can Found in general textbooks such as &quot; Optics &quot; by E, Hecht and A. Zajac, published by Wiley in 1979, pages 312-313. These simulations can be extended to many different structures and are not limited to the following example. The structure simulated in this example is shown in Figure 3. The substrate 33 is silicon, and an optimal SiO2 layer 34 is grown on the top (the bottom of FIG. 3 is shown in FIG. 3B), followed by a thick bottom layer and an image photoresist 31. The parameters to be discussed are oxide thickness and underlying optical constants! !,] &Lt;; and film thickness d. The photoresistance index η, the refractive index k and the film thickness d are fixed, such as η = 1.78, k = 0_018 ′ d = 2000 Α. In this example, three different underlying ARC thicknesses are simulated, namely d = 3000, 5000, 7000 A. The performance of a two-layer system is defined by the low (R2) substrate reflectance, which shifts when the swing ratio amplitude is reduced as defined in Equation 1. "Figure 3A. Shows n (ARC layer) in a 3000 A thick bottom layer (ARC). An analog substrate reflectance profile (a profile of constant R · 2) as a function of k (ARC layer). For example, the horizontal line k = 〇 24 intersects with several reflectance profiles 0.007 is the worst case. Because the reflectance of Jane is about 0.7 at 248 nra, we can get the reduction of swings <^ 75 ^ 75 ^ 57 = Figure 3 also -16- This paper size is applicable to Chinese national standards (CNS) A4 said grid (2 丨 〇〆 297 public 4) ---; -.-- ^ --- r-^-{Please read the notes on the back before filling out this page) Order printed by Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 4 June 4 R revised / corrected, supplemented the patent application No. 87113920 Δ γ Chinese manual amendment page (July 90) B7 V. Description of the invention (14) When the 10x swing ratio is reduced, it is allowed from ~ 丨, 65 to ~ 196 For a larger range of refractive index values, if a higher swing ratio reduction is required, the index value can be expected to be about 1.85. The k (ARC) value range near the optimal value is usually obtained from these simulations, and the decrease in the swing ratio is related to the size index. Figure 3B shows the reflectance profile of the oxide thickness as a function of k (ARC). As mentioned above, when the 1 Ox swing decreases, k = 0.24 and R &lt;? = 0.7%.

Figure 4 (Figures 4A4B and 5A and 5B correspond to Figures 3A and 3B respectively) show the simulation results of a 5000 A thick bottom layer. In the following arguments that are the same as above, the desired values of n (ARC) and k (ARC) are in the ranges of 1.70 to 1.90 and 0.15 to 0.22 ', respectively, and R &lt; = 0.3% when the 15χ swing ratio decreases. Similarly, Figure 5 shows that a reduction of the 25χ swing ratio is obtained at 7000 A thick ARC, while the values of η and k are approximately 1.84 and 0.11, respectively. It should be noted that these contour maps indicate that a wider range of values of η and k can be selected to obtain a larger swing ratio reduction (ρ1〇χ), and the figures derived above are for illustration purposes only. Finally, in order to achieve a high level of planarization, the minimum film interference should be 5000 A thick or higher. Example 2 This example shows how to adjust the optical properties of the thick bottom layer to obtain a very low swing ratio in a wider process window, with a thickness of about 150 A with n = 1.83 and k = 0,29 5 The thin adhesive layer is first deposited on silicon (refer to Table 1 in Figure ^). The second layer, preferably a fluorocarbon film, is deposited on it. This layer is about 5000 A thick. In this case, the adhesive layer prevents the fluorine deposition of the thick ARC layer from attacking the silicon substrate or Si02. The low refractive index of fluorinated carbon films usually helps to match the indices of Jane and SiO2. The third layer has a refractive index of about n = l.78. -17- This paper size applies to Chinese national standards (CNS &gt; A4ii grid (210X297 mm) I: ------ ^ --- .. ΛI — (Please read the note on the back of the page first, and then fill out this page), ιτ_ Yan, invention description (15 A7 B7 Ministry of Economic Affairs tYoung 槔 # 扃 The number of printed men ’s consumer cooperatives and the disappearance coefficient of about k = 0.21 , Then deposited on top to better match the optical constant of the photoresist. Figure 6 shows the simulated reflectance profile of this structure. By comparing this tunable structure with the single-layer structure of Figure 4, the process window can be greatly improved. The area of the reflectance profile of the tuned structure is approximately double that of the single-layer structure in Figure 4. Therefore, the same argument of use case i can be calculated to reduce the swing ratio by about 27. Table 1 shows that by using a fluorocarbon film, the A wide range of low index and high disappearance coefficient achieved. Example 3 The following example illustrates the process of depositing a hydrogenated and fluorinated amorphous carbon film (used as a thick underlying ARC) in a substrate (silicon is preferred). It is similar to plasma enhanced chemical vapor deposition (Pecvd) by cyclohexane gas or HFB. The simulated optical characteristics were performed. These experiments were performed to deposit an amorphous carbon film on a 5 or 8 inch pair of circular silicon substrate. The substrate, which was pre-cleaned, was blown dry with (filtered) nitrogen gas. In order to remove the residual particles before loading the cathode of Figure 1. Therefore, the system was evacuated to a bottom pressure reading of approximately 1 × 5 Torr or lower. The power density was 0.4 W / cm2 at a pressure of 100 mTorr Ar. The substrate was sputter cleaned for one minute to ensure good carbon film adhesion to the silicon substrate. An amorphous carbon film was deposited from the ring-burned gas at a flow rate of 25 sccm. A cathode power density of 0.62 w / cm2 would result in- Negative self-bias voltage of 317 volts, and the pressure is 100mTrr. The substrate is maintained at 59 during the entire deposition process. If a fluorinated film must be deposited, it can be used as; fluorinated benzene / hydrogen Mixture to replace cyclohexane. Table is a summary of the process parameters used (Figure 11). The gas used in this process has a purity of greater than about 99.99%. An amorphous carbon film is deposited at a rate of about 2 liters A / min at- 18-This paper size is applicable to China National Standards (CNS) A4 (2I0X297) %)

---- ^ 装 —:-(谙 Please read the notes on the back before filling in this page. J Type-I I I-二 ·

1 I * I · Indun d6B209 A7 _____B7, Central Industry Bureau of the Ministry of Economic Affairs, Consumers Cooperative V. Description of the invention (16> 'in the substrate. Example 4 The following example shows how to measure the optical properties of the deposited amorphous carbon film The constants n (ARC) and k (ARC) are vapor-deposited from a cyclohexane gas. This measurement technique can be applied to many different processes, and is not limited to the above two examples. Use n &amp; k Technology, S. Clara, Ca., n &amp; k spectrometer to measure optical constants. For a description of this instrument and its operation, refer to US Patent No. 4,905,170, 1990. It uses a Method to derive the optical constants of Forouhi and Bloomer (Phys. Rev. B, 28, pp. 1 865-1 874, 1988). The analysis is based on a physical model of the refractive index η and the disappearance coefficient k, which is applicable to a wide range of semiconductors And dielectric film range, and JL is effective in the deep ultraviolet near infrared wavelength range. The η (λ) and k (λ) (λ is the wavelength) spectrum of any material cannot be directly measured, but R (λ can be measured by the reflectance ) To determine. This measurable quantity depends on the film thickness' optical constants of the film and substrate. &Quot; n & k method &quot; provides a correct 'fast' and non-destructive way to interrupt reflectance measurements. Can produce Algorithm to compare the theoretical reflectance with the measured reflectance, from which the film thickness, η (λ) and k (; l) spectra can be determined. Figures 7, 8 (above) are shown for the amorphous carbon film. The reflectance spectrum (from 900 to 190 nm) measured by the n &amp; k analyzer is used as the thick ARC deposited by the third method. The analyzed film is about 5000 and 10000 A thick. Figures 7 and 8 (bottom) The corresponding values of n and k are displayed. In these particular examples, n is varied from ~ 1.80 to ~ 1.82, and k is ~ 0.22 at 248 nm. This paper is a common Chinese national standard (CNS) A4. Specifications (210X 297mm) (谙 Please read the notes on the back before filling this page} 装 '

.1T Α7 Β7 4 6 Revised page of Chinese Manual for Patent Application No. 1Π920 (July 1990) V. Description of Invention (17) (Please read the notes on the back before filling this page) Change to ~ 0.25 , Which is compatible with the reflectance analysis of the example. The n &amp; k spectra of Figures 7 and 8 also indicate acceptable values of n and k, which were obtained at 193 and 365 nm as described in Example 1. Finally, the calculated transmission curves (Figures 7 and 8 (above)) show that from 500 to 700 nm, the transmittance varies from 20 to 70% for a 1000a thick film, while at 1000A The change from 32 to 80% for thick films. These transmittance values are acceptable for correct mark alignment in multilayer semiconductor wafer manufacturing. Example 5: Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs This example shows how to use the above-mentioned double-layer photoresist system to form device characteristics below 0.25 μm. Figure 9 shows the manufacturing process. First, a thick amorphous carbon film 92 as described in Example 3, which is about or larger than 3,000 a, is deposited on a silicon substrate 93 'which has optical constants n and k of about 1.8 and 0.3, respectively. A thin ~ 2000 A is preferably a silicided photoresist 91 which can be spin-coated on top and 90 °. (: Bake for 90 seconds (Figure 9.1) such as Panjun varnish 'Polyhydrogen styrene, alternative polyoxy styrene polysilicone', polysiloxane, polyphenoxane, etc., a specific example is polyhydrophenoxy Alkanes), poly (cyclohexamethyloxane, 2,1,5-methylene) which includes polymethyloxane and the like. The silicided photoresist 91 was exposed to 248 nm radiation at a dose of approximately 38mJ using a Nikon EXX stepper, and baked at i20 ° C for 90 seconds. Then develop the photoresist in a CD26 Ship Developer (Fig. 9.2) for 30 seconds. Finally, the amorphous carbon film 92 was etched by reactive ion in an oxygen plasma at 50W under a pressure of 25 Mtorr for 15 minutes. The function of the resistor 91 is to etch the mask because it does not etch in the oxygen containing plasma (Figure 9_3). The SEM image of the etched double-layer structure is shown in Figure 10. The boundaries between silicified photoresist and thick bottom orbit are clearly visible. Note that the bottom carbon arc is an anisotropic etch, so wall verticality can be maintained. -20- This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) V-'711392〇 Chinese patent application manual amendment page (July 90) Α7 Β7 V. Description of invention (18 tlOa display 250 nm photoresistance line. The smaller line printed here is about 175 nm with an aspect ratio of 2: 3 (figure 〇b). The visible "grass" on the substrate comes from oxygen plasma etching Silicon contamination that contains photoresistors during this period can be removed by extremely short exposure to very low density fluorine containing plasma, or use longer development time before oxygen RIE. Although it has been specifically referred to its preferred embodiment The present invention is shown and explained, but those skilled in the art should understand that the detailed changes in the above and other forms can be implemented without departing from the spirit and scope of the present invention. Therefore, the present invention has been explained.丨 ^ ^ --- Installation-(I first read the note on the back of the? 1, and then fill out this page) Symbol description for printed components of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 10 Reaction chamber 11 Throttle valve 12 Spray head 13 Matching box 14 RF source 15 Substrate 16 Plate 17 Photoresistive heater 19 Cathode 20-26 Conduit 27 Photoresist layer 28 Polymer 29 Substrate 31 Impedance &gt; 1T · &gt; -21- This paper is scaled by CNS (210X297mm) ~ ~~-—III i 夺得 厶 厶 v :.-: One m rabbit Α7 Β7 5 82 0 ref. 87114920 Patent Application Chinese Manual Correction Page (July 1990) V. Description of Invention (18a) Central Ministry of Economic Affairs Printed by Standard Bureau of Shellfish Consumer Cooperative 32 ARC bottom layer 321 ARC upper layer 25nm 322 ARC upper layer 500nm 323 ARC adhesive layer 1 5nm 33 Si02 34 Si substrate 91 photoresist layer 92 DLC 93 substrate 151 Impedance: positive thickness = 850nm 152 first Layer: User-defined thickness 153 Second layer: Si dioxide thickness 154 Substrate: Silicon 300nm lOOnm HI— til · fltt ttl · — It 1 tut-1 In- ”-. Λ (Please read the precautions on the back first (Fill in this page again); &gt; · -21a- This paper size applies to China National Standard (CNS) A4 (2 [0X297mm)

Claims (1)

Ningyang Bureau of Standards, Ministry of Economic Affairs, Bei X Consumer Cooperatives Co., Ltd. d 6 8 ^^ 13920¾¾¾ ^^ A8 Revised Patent Application Scope (July 90) § __________ D8 VI. Patent Application Scope 1. A multilayer photoresist system structure, Including: a substrate having a plurality of surface layers, the plurality of surface layers are located on at least one major surface of the substrate, and the surface layer has at least one vapor-deposited anti-reflection coating layer; the gas deposition material is similar to Diamond carbon (DLC), fluorinated similar to diamond break (FDLC), fluorinated hydrogen similar to diamond carbon (FHdLC), nitrided similar to diamond carbon (NDLC), amorphous fluorinated hydrogen broken, amorphous fluorinated carbon, fluorinated carbon on all sides · 'Amorphous Nitriding Complete' Amorphous Nitriding Carbon, Nitrided Carbon, Nitrided Tetrahedron Carbon, and a combination of the above substances are selected from the group. 2. The multilayer photoresist system structure of item 1 in the scope of patent application, wherein the anti-reflection coating is a bottom layer, which is coated thereon with a layer of energy-activating material. 3. The multilayer photoresist of item 1 in the scope of patent application System structure, where the substrate is selected from the group consisting of a semiconductor, a polymer, glass, a metal, and a combination of the foregoing. 4. The multilayer photoresist system structure according to item 2 of the patent application range, wherein the energy-activating material comprises a silicided photoresist in the form of a dry plate. 5. For example, the multilayer photoresist system structure of the second patent application scope, wherein the energy-activating material and the bottom interface have a reflection ratio of about 0.000 丨. 6. The multi-layer photoresist system structure of the patent application No. 2 has a swing ratio reduction of at least about 25 or more. 7 &apos; The multilayer photoresist system structure of item 3 of the patent application scope, wherein the substrate is a semiconductor containing silicon. S. The multilayer photoresist system structure according to item 2 of the patent application range, wherein the energy-activating material is selected from the group consisting of: at uV wavelength ---------- 4-- this paper scale逋 Using Shen Guogu's home sample rate (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page} ----------- y ^ --- Ί.— —-. A8 B8 C8 D8 〇9 6. The scope of patent application (please read the precautions on the back before filling out this page) are sensitive compositions in the DUV wavelength range garden, which are sensitive compositions in UV and DUV The composition that is sensitive in the wavelength range, and the combination of the above-listed compositions &lt; &gt; Finely adjusted to substantially match the substrate at the first interface between the anti-reflection coating and the substrate, and the energy at the second interface between the anti-reflection coating and the energy activating material Activated materials. 10. For example, the multilayer photoresist system structure of the scope of patent application No. 1, wherein the anti-reflection coating contains a Carbon material. 11. The multilayer photoresist system structure according to item 9 of the patent application, wherein the anti-reflection coating is substantially uniform in thickness and optically non-uniform, with a graded refractive index and a graded disappearance coefficient β 12 For example, the multi-layer photoresist system structure of the patent application No. 9 wherein the refractive index can be adjusted to between about 1.4 and about 2.1 at 365, 248, and 193 nm. Printed by K-Industry Cooperative, Central Building Standard Bureau, Ministry of Economic Affairs 13. If the multilayer photoresist system structure of item 9 of the scope of patent application is applied, the disappearance coefficient can be adjusted to between 0.1 and about 0.6 at 36S '248 and 193 nra. Multi-layer photoresist system structure, wherein the refractive index can be adjusted to about 1.5 at the first interface to substantially match the main surface of the substrate, and can be adjusted to about 1.8 at the second interface to make the energy Matching activated materials with their contacts "15_Such as the application of the multilayer photoresist system structure in item 9 of the patent scope, in which the elimination is applicable @ 国 样 准 （CNS） A4 Lin （嫠） Beijing Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Policy A8 BS C8 D8 VI. The patent application scope loss coefficient can be adjusted to about 0.5 at the first interface to match the main surface of the substrate, and can be adjusted to about 01 at the second interface so that The energy-activating material matches its contacts. 16. The multilayer photoresist system structure of item 1 in the scope of patent application, wherein the vapor deposition material includes a dopant. 17. The multilayer of item 10 in scope of the patent application Photoresist system structure, in which the vapor deposition material can be patterned, and can be removed by reactive ion etching in an oxygen-containing gas and a combined gas. 18. The multilayer photoresist system structure according to item 16 of the patent application range, wherein the anti-reflection coating comprises a single-layer film of uniform thickness, the film having a refractive index of 1.42 to about 2.1 at a wavelength of 365,248, 193 nm, and A disappearance coefficient of about 0.001 to about 0.6. 19. For example, the multilayer photoresist system structure of the patent application No. 10, wherein the anti-reflection coating has a refractive index in the range of about 1.6-1.9, a disappearance coefficient of about 0_22 at 248 nm, and a coefficient of 300 nm. Even thickness. 20_ The multilayer photoresist system structure of item 19 in the scope of patent application has a swing ratio reduction of about 10. 21. The multilayer photoresist system structure according to item 10 of the patent application range, wherein the anti-reflection coating has a refractive index in the range of about K6-1.9, a disappearance coefficient of 0 1 5 at 24 ^ nm, and 5 0 0 nm average sentence thickness β 22. Such as the multilayer photoresist system structure of the scope of patent application No. 21 &amp; 'which has a swing ratio of about 15 reduced β 23. Such as the multilayer photoresist system structure of scope of the patent application No. 10 , Of which the anti-reflection coating has a refractive index in the range of about 248 nm (please read the precautions on the back before filling in this book) 4 .6 82 09 A8 B8 C8 D8 Printed by the J Industry Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 6. Scope of patent application The disappearance coefficient is about 0′12, and the uniform thickness is 700 nm. 24. The multilayer photoresist system structure according to item 23 of the patent application ', which has a swing ratio reduction of about 25. 25. If the multilayer photoresist system structure of item η in the scope of the patent application is applied, wherein the refractive index of the level index is about 1.4 to about 2_ h 26. Such as the multilayer photoresist system structure in the scope of patent application, the item 11 The state disappearance coefficient is about 0.6 to about 0,12. 27. The multilayer photoresist system structure of item u in the patent application, wherein the anti-reflection coating has a uniform thickness of about 10 to about 10,000 nm on a substrate. 28 · — A kind of double-layer photoresist system structure, in which the first layer of a thick bottom anti-reflection coating layer has a refractive index in the range of about K5-1.7, and disappears in the range of about 0.25-0.45 The coefficient, and the thickness of about 300 to 700, and the thickness of the melons are deposited on the first major surface of a substrate. 29. The double-layer photoresist system structure of claim 28, wherein the two layers of the thick bottom anti-reflection coating layer include DLC, FDLC, FHDLC, ndlc, amorphous fluorinated hydrogenated carbon, and amorphous fluorination. Carbon, tetrahedron fluorinated carbon, amorphous carbon nitride, amorphous carbonitrided hydrogenated carbon, nitrided tetrahedron carbon, and any combination of the foregoing are selected from the group consisting of materials. 30. The double-layer photoresist system structure according to item 29 of the patent application park, wherein the material of the thick bottom anti-reflection coating layer includes a dopant, which is selected from the group consisting of oxygen, silicon, or a mixture. The 28-layer photoresist system structure of the patent application Fanyuan, wherein the second layer of the thick bottom anti-reflection coating layer has a refractive index of about 18 and the paper is misaligned with Chinese National Standard (CNS) A视 # (210X297 ^ ％) (谙 Please read the notes on the back before filling in this page). Ordered by the Zhenggong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed on 6 8 2 〇 9 Β8 D8 6. The disappearance of the scope of patent application 0.21 Coefficient, and a thickness from about 20 to about 100 nm, and is deposited on a second major surface of the substrate and covered with a light emitting material. 32. A multilayer photoresist system structure, wherein the refractive index and the extinction coefficient in at least one thick bottom anti-reflection coating layer smoothly change from a low value to a higher value with the thickness of the coating. 33. The multilayer photoresist system structure as claimed in item 32 of the patent application scope, including at least one layer of a thick bottom anti-reflective coating layer, which has a refractive index of about 1.8, a disappearance coefficient of about 0.3, and from about 2 to about 30 nm thickness. 34. The multilayer photoresist system structure of item 32 of the patent application, including at least one additional layer of a thick bottom anti-reflection coating layer, which has a refractive index in the range of about 1,5-1.9, and in the range of about 0.15- The disappearance coefficient in the 0.5 range, and a thickness of about 100 to about 300 nm. 35. If the multilayer photoresist system and structure of item 32 of the patent application scope includes at least one additional layer of a thick bottom anti-reflection coating layer, it has a refractive index of about i.8, a disappearance coefficient of about 0.2 1, and Thickness of about 1000 to about 1000A β 36. The multilayer photoresist system structure of item 32 of the patent application scope includes at least one layer of a thick bottom anti-reflection coating layer, wherein the refractive index is smooth from about 1.9 The ground gradient is about 1.5 »37. The multilayer photoresist system structure of item 32 of the patent application scope includes at least one layer of a thick bottom anti-reflection coating layer, wherein the extinction coefficient smoothly changes from about 0.15 to about 0.5. 38. — A method for manufacturing a dry-deposited anti-reflection coating film on a substrate, including: _____________ This paper size is based on the Chinese national standard (CNS> Α4 wash grid (2i0X297 mm) (please threshold first) Read the notes on the back side and fill in this 萸) Order · ABCD 46 82 09 VI. Scope of patent application A substrate is mounted on an electrode in a chamber to deposit the anti-reflection coating film; the chamber is evacuated; Pre-cleaning the substrate and heating it; introducing dry-deposited anti-reflective coating layer · generating gas; energizing the chamber at a power density and / or sufficient time to deposit an anti-reflective coating layer to form a coating Cloth substrate; and removing the coated substrate β from the chamber. 39. The method of claim 38, wherein the substrate is a semiconductor substrate. 40. The method of claim 38, The chamber includes a reactive splash chamber β 41. The method of item 38 in the patent application, wherein the evacuation of the chamber includes evacuation to about 1 (Γ3 and about ΗΓ7 Torr. 42_ 如 应用Patent Fan Yuan No. 38 method, of which Aerating the substrate comprises adding the substrate to a temperature of about 25 to about 400 ° C. 43. The method of claim 38, wherein the pre-cleaning the substrate comprises rf splash cleaning the substrate. 44. A method as claimed in item 38 of the patent application, wherein the introduction of a vapor-deposited thick bottom anti-reflective coating layer-generating gas includes the introduction of hexafluorobenzene gas β 45. A method as claimed in item 44 of the patent application, wherein The step of introducing HFB gas further includes introducing a hydrocarbon gas and adjusting the relative amounts. The refractive index in the thick bottom anti-reflective cloth layer is lower, and the lower amount is the relative increase of HFB. National Standards (CNS) .A4 (210X297 mm) (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ---. 1 ------ ^ Order 1 ------ 1 7 ------------------ 468209 The scope of patent application The method of the ABCD machine for item 44 of the patent scope further includes introducing the dopant level of the gas into the chamber during the deposition, and the gas is selected from the group consisting of krypton, oxygen 'and a combination thereof. 47 'A manufacturing method for manufacturing a multilayer photoresist system structure, including the following steps: °' Providing a substrate; depositing a thick bottom anti-reflection coating layer on the substrate; spin-coating a shattered photoresist layer on top Bake the photoresist layer at 90 ° C for 90 seconds; expose to DUV through a photomask, and bake the photoresist layer for 90 seconds after i2 (rc); develop the silicided photoresist layer to form a Photoresist pattern structure; use the pattern silicified photoresist as an etching mask to etch the thick bottom anti-reflective coating layer in reactive oxygen and / or fluorine containing plasma to form a high aspect ratio of 250 nm 48. If the structure of item 1 of the scope of patent application 'where the substrate is selected from the group consisting of magnetic heads, electronic wafers' circuit boards, and semiconductor devices Structure, in which the energy-activating material is sensitive to energy, and the energy is selected from the group consisting of electromagnetic radiation, microbeams, and heating. C 50, as in the structure of the 49th scope of the patent application, wherein the microbeam is a Electronic Beams The structure of item μ of the utility model, in which the dopant is selected from the group consisting of oxygen, dreams, and their combination ... This paper is based on the Chinese National Standards (CNS) 8-4 (210X297 ^ cent) (Please Please read the notes on the back first and fill in the original form) ilir · Liji Ministry _ Printed by the Oac Industrial and Consumer Cooperatives A8 B8 C8 D8 Printed by the Central Government Bureau of the Ministry of Economic Affairs Consumer Cooperatives 8208 6. Application Patent scope 52_ Method of applying for patent scope item 38 'wherein the heating is selected from the group consisting of optics, photoresistance and their combination. 53_ Method of applying for patent scope No. 38 category, The anti-reflection coating layer is deposited at a rate of about 2 to about 200 nm / min, and reaches a total thickness of the bottom anti-reflection coating layer at a thickness of about 100 to about 10000 nm. 54. Structure, wherein the at least-vapor-deposited anti-reflection coating has a preset refractive index profile, a preset vanishing coefficient profile, and a preset thickness. 55_ The structure according to item 1 of the scope of patent application, wherein the At least one vapor-deposited anti-reflection coating is obtained by plasma deposition. The deposition coating, base-deposition deposition, ion beam deposition, evaporation, and the combination thereof are selected from the group consisting of 56. The structure according to item 1 of the scope of patent application, wherein the at least one vapor deposition anti-reflection coating is fine optical 57. The method according to item 38 of the patent application, wherein the excitation of the chamber is by a method for depositing the anti-reflection coating layer, which is deposited from plasma deposition, sputtering deposition, ion beam deposition, and evaporation. Select from the group of mergers. 58. If the method of the scope of the patent application is 38, it further includes introducing a dopant. 59. If the method of the scope of the patent application is 38, the anti-reflection coating layer is deposited to It has a controlled thickness, refractive index, and disappearance coefficient ^ 60. For example, the structure in item 1 of the patent scope, wherein at least one of the refractive index and the disappearance coefficient has a non-uniform profile. (Please read the notes on the back before filling in this X) The scale of this paper is applicable _ national standard of house ladder (0?) 8 4 specifications (210 father 297 mm)