JPH11150115A - Multilayered structure and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a resist which has superior optical purity and high adjustability and consists of a plurality of layers by forming an antireflection film on a substrate through vapor deposition. SOLUTION: After an amorphous carbon film a-C:X:H containing hydrogen and fluoride is stuck to a substrate by plasma-intensified chemical gaseous-phase vapor deposition, a photoresist PR containing silicon is applied to the surface of the carbon film a-C:X:H with a spin coater and baked. Then, after the photoresist PR has been developed with a developing solution, the carbon film a-C:X:H is subjected to reactive ion etching in oxygen plasma. As a result, the carbon film a-C:X:H functions as an ideal thick planarized lower antireflection film in a two-layer resist system for ultraviolet and far-infrared rays and can improve line width control and the performance of an integrated circuit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an integrated circuit (IC).
Structures, particularly those having multiple layers, and also having an adjustable thick underlayer coating based on an amorphous carbon film used in a two-layer resist system, and structures thereof Disclosed are methods useful for producing

[0002]

2. Description of the Related Art When a device size of a logic chip and a memory chip is reduced to about 0.25 μm or less, a currently used single-layer resist is useless in a general exposure apparatus. It is well known that reflection of a substrate at ultraviolet (UV) and deep ultraviolet (DUV) wavelengths results in standing wave effects and resist notching that severely limit critical dimension (CD) tolerances. Notching is caused by substrate topography and non-uniform substrate reflectivity that causes local changes in exposure energy on the resist. The standing wave is
Thin film interference (TFI), that is, a periodic variation in light intensity in the thickness direction of the resist. These light fluctuations occur because the planarization of the resist gives different thicknesses depending on the underlying topography. Thin film interference plays a dominant role in CD control of single layer photoresist processes, causing large variations in effective exposure dose due to small variations in optical phase.

[0003] Linewidth control is one of the most important requirements of an effective microlithography process. A typical criterion is that the drawn line width must be within 10% of the target value. There are many process variables that cause line width variations. FIG. 17 shows a simulation of how the line width of the resist varies depending on the exposure energy. Exposure energy of about 10 mJ / cm ² draws a line that is quite close to the target dimension of 0.25 μm. The underexposure state of 8.5 mJ / cm ² is equivalent to 0.
A line of 4 μm is drawn, and a line of 0.14 μm is drawn in an overexposure state of 12.5 mJ / cm ² . The only way to write the desired 0.25 μm line within the ± 10% criterion is to carefully control the exposure energy.

[0004] Unfortunately, there are many process factors that can affect the exposure energy in the photoresist.
The most important cause of such exposure variation is “Optim
Ization of optical property
ties of resist process
s ", (T. Brunner, SPIE Processe
ings Vol. 1466, p. 297,199
As described in 1), this is due to the thin film interference effect. Thin films used in semiconductor manufacturing, such as silicon nitride or silicon oxide, have some variation in thickness, which leads to variations in exposure energy entering the resist. If the photoresist is on silicon oxide of varying thickness, consider what varies and how, as shown by simulation. FIG. 18 shows the total reflectance of the wafer as measured by oxide (layer #).
It is shown as a function of the thickness of 1). Significant sinusoidal variations are observed with a maximum reflectance of 50% and a minimum reflectance of about 20%. FIG. 19 shows the calculated resist linewidth as a function of oxide thickness, and shows that the linewidth is significantly affected by small thickness variations. A comparison between FIG. 18 and FIG. 19 shows that the line width is small (overexposure) when the reflection of the resist is small, and the line width is large (underexposure) when the reflection of the resist is large. The basic mechanism is that thin-film interference causes the exposure energy in the resist to vary with oxide thickness.

An anti-reflection film (Anti-Reflecto)
r Coat) or ARC is used to reduce such effects. Thus, consider an example having a carbon ARC. FIG. 20 shows the upper resist and ARC layer #
1 shows a thin film stack having 1, an oxide layer # 2, and a silicon substrate. FIG. 21 shows the reflectivity of the resist,
Shown as a function of oxide thickness. The presence of the ARC causes the reflectivity to be about 8%, which is almost independent of oxide thickness. This indicates that even if the oxide thickness varies considerably, the exposure energy does not vary. As expected, the line width versus oxide thickness curve in FIG. 22 is almost flat. The entire range of data easily meets the ± 10% line width control criteria.

Current semiconductor processes often have many thin films of varying thickness, and the photoresist film itself also varies in thickness. The ARC layer is generally applicable to line width reduction depending on the thickness of many layers in the process stack. The carbon ARC given in this patent application is a particularly attractive means, as explained in detail.

In order to overcome these problems, here,
A multilayer resist system is disclosed. In this method, UV
-A first thick lower polymer layer absorbing DUV is spin-coated on the substrate. This layer has the effect of flattening the lower structure to reduce thin-film interference and the effect of weakening the reflection (notching) of the substrate. A second thin Si-containing resist layer is spun on top. This thin layer is used as a high resolution image forming layer,
After resist development, it is used as a transfer pattern layer for oxygen reactive ion etching. The lower layer is not attacked by the developer and the upper layer of the resist is not etched by oxygen plasma due to its Si component. This process is described in more detail in Example 5. For an overview of multilayer resist technology, see "Polymeric silicone"
n-containing resist material
ial ", RD Miller and GMW
allraff, Advanced Material
s for Optics and Electroni
cs, Vol. 4, 95-127 (1994). The lower layer currently used is "Bi
layer resist approach for
193 nm lithography ", Scha
edley et al. Proc. SPIE-In
t. Soc. Opt. Eng. (USA) Vol. 27
24 No. 24, 1996, p344-54. This "spin coating (spin coating)
on) "A major problem associated with polymeric materials is poor conformality on sub-micron structures.
rmality), poor optical tunability, and chemical interactions that cause critical dimension (CD) variations at the interface with the imaging resist.

[0008] When a thick single layer resist is used instead of two layers, mechanical destruction of the resist pattern may occur, as described in the "Characterization of the resist".
eresist pattern collapse
in a chemically amplified
resist ", Cha-Won Koh, Cheo
ul-Kyu Bok, and KiHo Baik,
Interface 1996 Proc. p295-3
02, S. Diego Ca. 1996.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved resist.

It is another object of the present invention to provide an improved resist having a plurality of layers.

Another object of the present invention is to provide a resist having a plurality of layers whose lower layers are thick adjustable layers.

It is an object of the present invention to provide a formation of a lower planarization layer by vapor deposition. The deposited films have much increased optical purity and tunability when used in two- and three-layer resist systems as compared to spin-coated polymers.

Another object of the present invention is to provide aC having the optical properties necessary to form a DUV (365, 248, 193 nm) underlayer in a two / three layer resist system:
An object of the present invention is to provide a method for depositing by depositing an H film. These films have a wide range of optical tunability, ie, n and k can be changed by changing the process conditions. These films can be easily anisotropically patterned and removed by oxygen plasma. This method can be easily extended to manufacturing equipment currently used in the semiconductor industry.

Another object of the present invention is to perform deposition by vapor deposition in a mixed gas of Ar / hydrocarbon / helium / hydrogen / fluorocarbon / nitrogen / oxygen. Preferably, the hydrocarbon is cyclohexane or acetylene, and preferably, the fluorocarbon is hexafluorobenzene. Higher refractive indices are obtained by limiting or eliminating the flow of hexafluorobenzene (HFB) in the plasma chamber. The smaller index is H
It is obtained by increasing the flow of FB and limiting or eliminating the flow of hydrocarbon gas. The large extinction coefficient k is
Obtained by depositing the film with a high cathode bias voltage. Smaller values of k are obtained by reducing the bias voltage. Subtle optical tunability can be achieved by using appropriate flow rates of nitrogen and / or oxygen. Hydrogen is used to adjust optical properties and film durability.

It is another object of the present invention to provide a method for use as a lower layer in a two-layer resist system having optical properties optimized to reduce reflections occurring at the substrate and at the resist / lower layer interface. An object of the present invention is to provide a method for depositing a shaped carbon film by vapor deposition. This lower layer acts as a thick planarized anti-reflective coating (ARC) and further reduces thin film interference. Process gas chemistries and process parameters are generally individually optimized to achieve the required optical properties.

Another object of the present invention is to provide a method for depositing a thick ARC layer whose refractive index n and extinction coefficient k vary over the depth of the film to form an improved anti-reflection film. It is in. As an example, ARC
2 shows that the layer is divided into three different layers having different optical properties. This layer is shown to have very low reflectivity and large tolerance for process variations. This deposition technique is described in SPIE Vol.
26, p. 573 (1996) ", which can be applied to layers whose optical properties vary continuously over the depth of the film. More importantly, technically thick ARCs Layer n and k
Is exactly equal to the n and k of the adjacent layers, there is no reflection and significantly improved CD control.

[0017]

SUMMARY OF THE INVENTION A broad aspect of the present invention is a multilayer resist system and a method of making the same.

A particular form of the invention is a multi-layer resist system,
AC: X: H with adjustable optical properties and
(Where X is fluorine, nitrogen, oxygen, Si) by vapor deposition. The obtained carbon film is composed of what is called diamond-like carbon or amorphous carbon.

Yet another specific form of the method and structure according to the present invention is to deposit from a hydrocarbon / fluorocarbon / hydrogen plasma having any small amount of nitrogen and / or oxygen, such as about 1 sccm per deposition. To deposit a hydrogenated carbon film. The film manufactured here has a refractive index n and an extinction coefficient k that can be independently adjusted at wavelengths of 365, 248, and 193 nm, and is extremely effective for a thick flat antireflection film. Further, films formed according to the present invention can be conformally deposited topographically and, when used as an underlayer in a multi-layer resist system, are easily patterned by an oxygen and / or fluorine reactive ion etching process. Or can be removed, thus facilitating patterning for chip fabrication.

Yet another specific form of the method and structure according to the present invention is to deposit an amorphous carbon film by vapor deposition, which comprises a hydrocarbon gas, a fluorocarbon gas, a hydrogen gas, and any small amount of oxygen gas. And / or premixing a nitrogen gas, preparing a reaction chamber including a cathode and a substrate, introducing the mixed gas into the chamber, applying an RF bias potential to the cathode to generate plasma, A- on the substrate by evaporation
Attaching a C: X: H film.

Another particular form of the structure and method according to the present invention is to deposit an amorphous carbon film by using a gas mixture. The gas mixture contains hexafluorobenzene, hydrogen, cyclohexane, and acetylene (which may or may not be diluted with He or Ar) and reactively deposits the film by vapor deposition. By using this method, the refractive index n and the extinction coefficient k
Can be adjusted optically independently at UV and DUV wavelengths. More particularly, UV and DU
The refractive index n and extinction coefficient k of V can be adjusted to about 1.4 to about 2.1 and about 0.1 to about 0.6 at 365, 248 and 193 nm wavelengths, respectively. Thus, these films meet all the requirements needed to be used as a thick planarizing underlayer in a two-layer resist system.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a structure and a method of manufacturing the structure. The structure may be multi-layer, preferably two-layer /
A high quality hydrogenated carbon film used as a planarized and optically tunable thick lower ARC in a three-layer resist system is produced by a method of vapor deposition with a hydrocarbon and / or fluorinated hydrocarbon (fluorocarbon) plasma. You. Films made in accordance with the present invention are optionally graded along film thickness to match the optical properties of the substrate and the imaging photoresist.
It has adjustable refractive index and extinction coefficient. Optical and lithographic features in UV and DUV of films made according to the present invention are described in D. M
iller and G.W. M. A by Wallraff
advancedMaterials for Opti
cs and Electronics, Vol. 4,
95-127 (1994), much better than those obtained with other polymer films such as diazonaphthoquinone-novolak type photoresists. Therefore, S coated with the thick planarized amorphous carbon film of the present invention
The i-substrate greatly reduces thin film interference and substrate reflectivity at UV and DUV wavelengths, thus improving CD control.

FIG. 1 illustrates a PECVD (Plasma Enhanced Chemical Vapor Deposition) deposition apparatus 8 that can be used to deposit the amorphous carbon film of the present invention. This device is
A reactor chamber 10 is provided having a throttle valve 11 separating the reactor chamber 10 from a vacuum pump (not shown). Cathode 19 is attached to reactor chamber 10 and is insulated from reactor chamber by dielectric spacer 27. The cathode 19 has a resistance heater 17. The substrate 15 is fixed to the inside end of the cathode 19. Cathode 19 is electrically connected to tunable radio frequency source 14, and the impedance between cathode 19 and radio frequency source 14 is matched by using matching box 13. An electrical return ground is provided by a plate 16 connected to the reactor chamber 10.

The reactor chamber 10 is provided with conduits 20, 21, 22, 23, 24, 25, for introducing various gas materials into the chamber 10 through the shower head 12.
26. For example, a hydrocarbon gas and a premixed hydrocarbon mixture gas are introduced into the reactor chamber 10 via lines 25 and 26. The fluorinated carbon gas and the hydrogen gas are introduced into the chamber 10 via the pipes 21 and 20, respectively. Reactive gases, oxygen and nitrogen, are introduced into chamber 10 via lines 23 and 22, respectively, while A
r gas is introduced via line 24.

The hydrocarbon gas used in the present invention can be any of the following hydrocarbon compounds. First, it can be gaseous, and second, it can form a plasma under the reaction conditions used by the process of the present invention. The term hydrocarbon means that the molecules forming the compound contain only carbon and hydrogen atoms. According to one embodiment of the present invention,
Saturated or unsaturated hydrocarbon compounds can be used by the process of the present invention. By definition, a saturated hydrocarbon compound is a compound in which the molecule contains only a single bond of carbon, while an unsaturated compound is a compound in which the molecule contains a double or triple bond of carbon.

In a particularly preferred embodiment of the present invention, suitable reactive hydrocarbon and fluorocarbon gases used to form the amorphous carbon film are cyclohexane and hexafluorobenzene, optionally diluted with an inert gas. (HFB). Further, it should be understood that mixtures of hydrocarbon gases such as cyclohexane / acetylene / methane can be used as the reactive hydrocarbon gas of the present invention.

The gas used in the present invention is about 95.5%
It has the above purity. In a preferred embodiment, the gas is about 9
It has a purity ranging from 8.5 to about 99.99%. Most preferably, the gas has a purity of 99.99% or higher.

First, a hydrocarbon gas, a fluorocarbon gas, a hydrogen gas, a helium gas, and an argon gas are about 1 m in length.
It is introduced into the chamber by passing through a separate flow controller at a flow rate sufficient to provide a total pressure of argon, hydrogen, hydrocarbons, fluorocarbons and helium of Torr to 1000 mTorr. To provide the most effective amorphous carbon films, argon, hydrogen, hydrocarbons,
The pressure of the helium mixed gas is about 1 to 500 mTorr
It is preferred that Further, the above-mentioned condition is that argon, hydrogen, hexafluorobenzene, hydrocarbon, and helium are mixed in one, two, or three gas cylinders.
It can be obtained by premixing in all possible combinations giving the desired gas concentration. More preferably, argon gas, hydrogen gas, fluorocarbon gas,
Hydrocarbon gas is introduced into the chamber via a separate flow controller.

Suitable substrates that can be coated with the amorphous carbon film of the present invention include plastics, metals, various types of glass, magnetic heads, electronic chips, electronic circuit boards, semiconductor devices, and the like. The substrate to be coated can be of any shape or size as long as the substrate can be placed in a reactor chamber apparatus. Thus, regularly or irregularly shaped objects having certain dimensions can be used in the present invention.
More preferably, the substrate is a Si substrate used for manufacturing a semiconductor device. The substrate is provided on a cathode holder inside the reactive sputtering chamber of the reactor apparatus. Next, the reactor chamber is hermetically sealed and evacuated to a pressure in the range of about 1 × 10 ⁻³ to about 1 × 10 ⁻⁷ Torr. After evacuating the reactor chamber to the desired pressure range described above, the substrate is then heated to a temperature of 25-400C. Most preferably, the substrate is maintained at a constant temperature between about 50 and about 200 C throughout the entire deposition process.

[0030] The substrate material used is RF-deposited using an RF cathode on the chamber prior to depositing the amorphous carbon film.
Sputter cleaning may or may not be performed. Suitable cleaning techniques used by the present invention include RF plasma cleaning with hydrogen, argon, oxygen, nitrogen, or mixtures thereof, which may be performed alone or in a suitable series of combinations.

After achieving the required exhaust pressure, the gas mixture is
It is introduced into the reactor chamber at a flow rate of about 1-1000 sccm. More preferably, the flow rate of the reaction gas is 1 to 10
0 sccm, and the flow rate of the hydrogen gas is 1 to 100 sc
cm. Most preferably, the flow rate of cyclohexane gas is about 5 seem. The gas is about 5-200mTo
It is introduced into the reactor chamber at a pressure of rr. In another aspect of the invention, the gas mixture is introduced at a pressure of about 100 mTorr.

Upon deposition, an RF bias was applied to the substrate provided on the cathode. The cathode DC self-bias voltage is -10 to -100 throughout the carbon deposition process.
It was in the range of 0V. This self-bias voltage was obtained by supplying RF power to the cathode. Radio frequency impedance matching was obtained by using an RF matching box. Most preferably, the RF bias voltage applied to the substrate is −30 throughout the experiment.
It was maintained at 0V. More preferably, the power density applied to the substrate is 0.005~5W / cm ^2. Most preferably, the power density used by the present invention is maintained at 0.62 W / cm ² throughout the deposition process.

[0033] The amorphous carbon film is deposited on the substrate at a rate such that a substantially continuous coating is obtained on the substrate.
In particular, by using the process parameters described above, the amorphous carbon film is deposited on the substrate at a rate of about 20-4000 ° / min. Most preferably, the rate of deposition of the amorphous carbon film on the substrate is about 1600 ° / min.

According to the present invention, the thickness of the amorphous carbon film deposited on the substrate is 1000-50,000 °. More preferably, the thickness of the amorphous carbon film is 3000 to 700
0 °. By changing process parameters such as bias voltage, gas flow, and pressure, the optical constants of the film can be changed. Here, the optical constant of the film is
Defined as refractive index n and extinction coefficient k. Therefore,
It is possible to produce substrates with defined optical constants by simply diluting cyclohexane or acetylene in Ar or He, or by changing cyclohexane to a gas mixture with HFB / hydrogen (Table 1). is there. The preferred optical constants of the amorphous carbon film as the lower layer in bilayer resist-based applications made according to the present invention are: k at wavelengths of 365, 248 and 193 nm.
= 0.1-0.6 and n = 1.40-2.1.

Primarily, the amorphous carbon film formed according to the present invention has UV (365 nm) and DUV (248
And 193 nm) can be used as an ideal thick planarized bottom anti-reflective coating for use in two-layer resist-based applications. "Spin on polymer
The advantage of carbon ARCs as compared to "polymers" is that they can be conformally deposited with significantly improved optical purity and tunability and integrity, thereby providing line width control and integrated circuits. The performance of the system can be improved.

It is well known that the effective exposure dose in optical lithography varies periodically with resist thickness due to thin film interference. The swing ratio S is defined as the ratio of the change in exposure between the maximum interference thickness and the minimum interference thickness. S is a basic measure of the quality of a particular resist process. By reducing the swing ratio to near zero, the resist process can tolerate resist-induced optical phase variations and deposited film thickness non-uniformity. The swing ratio can be calculated by the following equation.

[0037]

(Equation 1) R ₁ is the reflectivity at the resist / air interface;
R ₂ is the reflectivity at the upper resist / ARC interface. α is the extinction coefficient of the resist, and D is the thickness of the resist. In the present invention, it has mainly interested in reducing the swing ratio by reducing the R ₂ using a two-layer resist process with respect to optimized the lower layer ARC. FIG. 2 illustrates the importance of the above parameters. In general, a dual resist system can be modeled to determine the optical parameters (n and k) and the optimal thickness of the underlying layer. In order to achieve this, it is necessary to know the optical constants of all film structures in order to calculate the swing ratio reduction.

In general, the thickness d of the ARC varies between 3000 and 7000 ° depending on the light absorption of the film. The extinction coefficient k varies between 0.11 and 0.5. More generally, the value of k is DU for a swing ratio reduction of 10.
V was 0.11 to 0.3. The refractive index n is 1.4
It fluctuates between ２．１2.1. More generally, the value of n is
DUV ranged between 1.65 and 1.90.

The following examples are given to illustrate the scope of the present invention. These examples are given for illustration only,
The present invention is not limited to this.

Example 1 The following example illustrates calculations to obtain optimal lower layer parameters for a two-layer system. The parameters are optimized to reduce reflection at the resist / underlayer interface. Calculations are based on Optics, by E. Hecht and
A. Zajac, published in 1979
Based on algorithms using Fresnel coefficients shown in standard textbooks such as by Wiley, pages 312-313. These simulations can be extended to many different structures and are not limited by the examples given below. The structure simulated in this example is shown in FIGS.

The substrate is silicon, with an optional SiO ₂ layer on top (FIG. 4), on which a thick lower layer and an image forming resist are provided. The parameters in this experiment were the oxide thickness and the optical constant n of the lower layer.
And k, and the film thickness d. The refractive index n, extinction coefficient k, and film thickness d of the image forming resist are constant,
n = 1.78, k = 0.018, and d = 2000 °
Given by In this example, three different lower layer ARC thicknesses, d = 3000, 5000, 7000, are simulated.

The quality of a two-layer system is determined by the low (R ₂ ) substrate reflectivity that contributes to the reduction in the magnitude of the swing ratio defined by equation (1). FIG. 3 also shows n (of the ARC layer) and k of the 3000 ° thick lower layer (ARC).
A function of (ARC of layers), shows a simulated substrate reflectivity equal contour plots of (contour lines of constant R _2). For example, the horizontal line k = 0.24 intersects some worst case reflectance contours 0.007. The reflectance of Si at 248 nm is about 0.7, and a reduction ratio (0.7 / 0.007) ^0.5 = 10 of the swing ratio is obtained. FIGS. 3 and 4 show that a swing ratio reduction rate of 10 is approximately 1.6.
A wide range of refractive index values from 5 to about 1.96 is acceptable.
If a larger swing ratio reduction is required, a value of the refractive index close to 1.85 is desirable. In general, these simulations provide a range of k (ARC) values that are close to optimal values by reducing the swing ratio by an order of magnitude or more. FIG. 4 shows the reflectance contour of the oxide thickness as k (AR
It is shown by the function of C). As described above, at k = 0.24, R ₂ ≦ 0.007, and the swing ratio reduction rate 10
Becomes

FIGS. 5 and 6 (corresponding to FIGS. 3 and 4)
Figure 4 shows simulation results for a 5000mm thick lower layer. Following the same reasoning as described above, with respect to R ₂ ≦ 0.003 as the swing ratio reduction rate 15, preferably n
The values of (ARC) and k (ARC) are 1.7
0 to 1.90 and 0.15 to 0.22.
Similarly, FIGS. 7 and 8 (corresponding to FIGS. 3 and 4) show that the swing ratio reduction rate 25 is about 1.84 and about 0.8, respectively.
7000 mm thick AR with n and k values of 11
It shows that C can be obtained. These contour plots show that a wide range of n and k values can be selected to obtain significant swing ratio reduction (≧ 10), and the above numbers are given for illustration. It should be noted that Finally,
To achieve a higher degree of planarization, ie, reduce thin film interference, the lower ARC layer is preferably 5000
The thickness must be at least Å.

Example 2 This example shows how a wider process window with very small swing ratio values can be obtained by adjusting the optical properties of the thick underlying layer. . n = 1.83 and k = 0.295
A thin adhesive layer of about 150 ° thickness having the following is first deposited on the Si (see Table 1 in FIG. 18). A second layer, preferably a fluorinated carbon film, is deposited on top.
This layer is approximately 5000 ° thick. In this case, the adhesive layer is made of a thick ARC layer made of a silicon substrate or SiO _2.
To prevent invasion. In general, the lower index of refraction of the fluorinated carbon film helps to match the index of refraction of Si with the index of refraction of SiO ₂ . A third layer having a refractive index of n = about 1.78 and an extinction coefficient of k = about 0.21 is deposited on top to better match the optical constants of the imaging resist. Simulated reflectance contours for this structure are shown in FIGS. Comparing this tunable structure with the single layer of FIGS. 5 and 6 results in a significant improvement in the process window. The area surrounding the reflectivity contour 0.001 of the adjustable structure is shown in FIG.
One order of magnitude higher than the single layer of FIG.
fmagnitude) large. Thus, a swing ratio reduction of about 27 can be calculated using the same reasoning as in Example 1. Table 1 (FIG. 18) shows that a wide range of low refractive index and high extinction coefficient can be achieved by using fluorinated carbon films.

Example 3 The following example demonstrates the formation of a hydrogenated and fluorinated amorphous carbon film (used as a thick underlayer ARC) on a substrate, preferably Si, with cyclohexane gas or HF.
FIG. 4 shows a process for deposition by plasma enhanced chemical vapor deposition (PECVD) in B. FIG. This film has optical properties similar to those simulated in Examples 1 and 2.

This experiment was performed to deposit an amorphous carbon film on a 5 inch (12.7 cm) or 8 inch (20.3 cm) round Si substrate. The pre-cleaned substrate was blow-dried with (filtered) nitrogen gas to remove residual particles before being placed on the cathode of FIG. After that, this system is about 1 × 10 ^-8 Torr
It was evacuated to a base pressure of r or less. The substrate was 100 mT to ensure good adhesion of the carbon film to the Si substrate.
The wafer was sputter-cleaned at an Ar pressure of orr and a power density of 0.4 W / cm ² for 1 minute. When the amorphous carbon film is 2
Deposited from cyclohexane gas at a flow rate of 5 seem. The power density of the cathode is 0.62 W / cm ² which produces a negative self-bias of −317 V and the pressure is 100
mTorr. During the entire deposition process, the substrate is 59
° C. If a fluorinated film must be deposited, the cyclohexane gas can be replaced with a mixed gas of hexafluorobenzene / hydrogen. A list of the process parameters used is shown in Table 1 (FIG. 18). The gas used in the process of the present invention is about 99.9
It has a purity of 9% or more. Amorphous carbon film is about 215Å
/ Min on the substrate.

Example 4 The following example illustrates the optical constants n (ARC) and k of an amorphous carbon film deposited by vapor deposition from cyclohexane gas.
It shows how (ARC) is measured. This measurement method can be applied to various different processes, and is not limited by the above two examples.

The optical constant is n & k Technology
y, S. N & k manufactured by Clara, Ca
It was measured using an Analyzer. A description of this device and operation is provided in U.S. Pat. No. 4,905,170. They are based on a broadband spectrometer-based method and the methods of Forouhi and Bloomer (Ph.
ys. Rev .. B, 38, pp. 1865-1874,
1988). These analyzes are based on physical models for the refractive index n and the extinction coefficient k and can be applied to a wide range of semiconductor and dielectric films, and are effective in the far ultraviolet to near infrared wavelength range. N (λ) and k (λ) of the material
The (λ is wavelength) spectrum cannot be measured directly, but is determined by the de-convolution of the reflectance measurement R (λ).
This measurable amount depends on the film thickness and the optical constants of the film and the substrate. The "n & k method" provides an accurate, fast, non-destructive way to uncouple reflectance measurements. An algorithm can be generated that compares the theoretical reflectance with the measured reflectance. From this comparison, the film thickness and n
(Λ) and k (λ) spectra can be determined.

FIGS. 11 and 13 show reflection spectra (900-190 nm) measured by an n & k Analyzer of an amorphous carbon layer used as a thick ARC deposited by the method of Example 3. FIG. The analyzed membranes are about 5000 and 10000 ° thick. The corresponding n and k values are plotted in FIGS. In these particular examples, at 248 nm, n varied from about 1.80 to about 1.82 and k varied from about 0.22 to about 0.25, which is consistent with the reflectance analysis of Example 1. The n & k spectra of FIGS. 12 and 14 show that the acceptable values n and k are 1 as described in Example 1.
It is shown that it can be obtained also at 93 and 365 nm.
Finally, the calculated transmittance curves (FIGS. 11 and 13)
Means that the transmittance between 500 and 700 nm is 20-70% for a 10000 mm thick film and 3 for a 5000 mm thick film.
2 to 80%. These transmittance values are acceptable for proper mark alignment in multilayer fabrication of semiconductor chips.

Example 5 This example demonstrates the use of the two-layer resist system described above,
3 illustrates a method for forming sub-μm device features. FIG. 15 shows a flow of the manufacturing process. First, as described in Example 3, a thick amorphous carbon film of about 3000 ° or more is deposited on a Si substrate having optical constants n and k of about 1.8 and 0.3, respectively. About 200 thin
A photoresist, preferably comprising silicon at 0 °, is spun on top and baked at 90 ° C. for 90 seconds (FIG. 1).
5 (A)). The resist may be novolak, polyhydroxystyrene, substituted polyhydroxystyrene polysilane, polysiloxane, polysilsesquioxane, etc. In particular examples, poly (4-hydroxybenzylsilsesquioxane), poly (cyclohexyl) Methylsilane), 2,1,5-naphthaquinone containing polymethylsiloxane, and the like. The resist containing silicon is Ni
Using a kon EXX stepper with a dose of about 38mJ
Exposed to 48 nm radiation and post-baked at 120 ° C. for 90 seconds. Next, the resist is CD26 Shi.
Develop for 30 seconds with pley developer (Fig. 15
(B)). Finally, the amorphous carbon film is reactive ion etched in an oxygen plasma at 50 W for 15 minutes at a pressure of 25 mTorr. Here, since the resist containing silicon is not etched by the oxygen-containing plasma, it functions as an etching mask (FIG. 15C). Observation of the etched bilayer structure by SEM clearly shows the boundary between the silicon-containing resist and the thick lower ARC. It should be noted that the bottom carbon ARC is anisotropically etched, thereby keeping the walls vertical. 2
The finer line drawn by the 50 nm resist line is about 175 nm and has an aspect ratio of 3 or more (FIG. 17). "Grass" generated on the substrate
s) "results from contamination of the silicon-containing resist during oxygen plasma etching and uses a very short exposure to a plasma containing a very low density of fluorine, or uses longer development before oxygen RIE. Can be removed.

In summary, the following matters are disclosed regarding the configuration of the present invention. (1) A structure including a substrate having at least one main surface, a plurality of surface layers, and at least one deposited antireflection film. (2) The structure according to (1), wherein the antireflection film is a lower layer covered with a layer of an energy active material. (3) The substrate is a semiconductor, a polymer, a glass, a metal,
And a structure selected from the group consisting of: and a combination thereof. (4) The structure according to (2), wherein the energy-active material is a silicon-containing photoresist in a dry sheet shape. (5) The structure according to (2), wherein a reflectance at an interface between the energy active material and the lower layer is about 0.001. (6) The structure according to (2), wherein the swing ratio reduction rate is at least about 1/25 or more. (7) The structure according to (3), wherein the substrate is a semiconductor made of silicon. (8) The energy active material is a composition sensitive to UV wavelength, a composition sensitive to DUV wavelength, UV and DU
The structure according to (2), wherein the structure is selected from the group consisting of a composition sensitive to V wavelengths and a combination thereof. (9) a refractive index and an extinction coefficient of the anti-reflection film, a first interface between the anti-reflection film and the substrate, and a second interface between the anti-reflection film and the energy active material; 3. The structure according to (2), wherein the structure is finely adjusted so that the refractive index and the extinction coefficient of the energy-active material and the substrate substantially coincide with each other. (10) The structure according to (1), wherein the antireflection film is made of a material containing carbon. (11) The antireflection film is characterized in that the thickness and the optical non-uniformity are substantially uniform due to a continuously changing refractive index and a continuously changing extinction coefficient. The structure according to 9). (12) The refractive indices are 365, 248, and 193.
The structure according to (9), wherein the wavelength is adjustable between about 1.4 and about 2.1 at a wavelength of nm. (13) The extinction coefficients are 365, 248 and 19
The structure according to (9), wherein the wavelength can be adjusted between about 0.1 and about 0.6 at a wavelength of 3 nm. (14) The refractive index is about 1.5 at the first interface so as to substantially match the refractive index of the main surface of the substrate.
(9) wherein the second interface is adjusted to about 1.8 at the second interface to match the refractive index of the energy active material in contact with the second interface. The described structure. (15) about 0.5 at the first interface so that the extinction coefficient matches the extinction coefficient of the main surface of the substrate.
(9) wherein the second interface is adjusted to about 0.1 at the second interface to match the extinction coefficient of the energy-active material in contact with the second interface. The described structure. (16) The deposition material is diamond-like carbon (DLC), fluorine-added diamond-like carbon (FDLC), fluorine- and hydrogen-added diamond-like carbon (FHDLC), nitrogen-added diamond-like carbon (NDLC) ), Fluorine and hydrogenated amorphous carbon, fluorinated amorphous carbon, fluorinated tetrahedral carbon, nitrogen-added amorphous carbon, nitrogen and hydrogenated amorphous carbon, nitrogen-added tetrahedral carbon, and combinations thereof The structure according to (1), wherein the structure is selected from the group consisting of: (17) The structure according to (16), wherein the vapor deposition material contains a dopant. (18) The structure according to (10), wherein the vapor deposition material can be patterned and removed by reactive ion etching using a gas containing oxygen, fluorine, and a combination thereof. (19) The antireflection film is formed of a single-layer film having a uniform thickness, and the single-layer films are 365, 248, and 193.
The above (17), having a refractive index in the range of about 1.42 to about 2.1 and an extinction coefficient in the range of about 0.1 to about 0.6 at a wavelength of nm. Structure. (20) The antireflection film has a refractive index in a range of about 1.6 to 1.9 at a wavelength of 248 nm, an extinction coefficient of about 0.22, and a uniform thickness of 300 nm. The structure according to the above (10). (21) The structure according to (20), having a swing ratio reduction rate of about 10. (22) The anti-reflection film has a refractive index in a range of about 1.6 to 1.9 at a wavelength of 248 nm, an extinction coefficient of about 0.15, and a uniform thickness of 500 nm. The structure according to the above (10). (23) The structure according to (22), having a swing ratio reduction rate of about 5. (24) The antireflection film has a refractive index in a range of about 1.6 to 1.9 at a wavelength of 248 nm, an extinction coefficient of about 0.12, and a uniform thickness of 700 nm. The structure according to the above (10). (25) The structure according to (24), having a swing ratio reduction rate of about 25. (26) The graded refractive index is about 1.4 to about 2.
The structure according to the above (11), wherein the number is 1. (27) The structure according to (11), wherein the graded extinction coefficient is about 0.6 to about 0.12. (28) The antireflection film is formed on the substrate by about 10 to about 100
The structure according to the above (11), having a uniform thickness of 00 nm. (29) The first layer of the thick lower antireflection layer has a thickness of about 1.5 to 1.5
A refractive index in the range of 1.7, an extinction coefficient in the range of about 0.25 to 0.45, and a thickness of about 300 to 700 nm;
A two-layer structure deposited on a first major surface of a substrate. (30) The two layers of the thick lower anti-reflection layer have a D
LC, FDLC, FHDLC, NDLC, fluorine and hydrogenated amorphous carbon, fluorine added amorphous carbon, fluorine added tetrahedral carbon, nitrogen added amorphous carbon, nitrogen and hydrogenated amorphous carbon, nitrogen added tetrahedral carbon, And the combination thereof. The two-layer structure according to the above (29), wherein (31) The two-layer structure according to the above (30), wherein the material of the thick lower anti-reflection layer contains a dopant selected from the group consisting of oxygen, silicon, or a combination thereof. (32) The second layer of the thick lower anti-reflection layer has a thickness of about 1.
8, a extinction coefficient of about 0.21 and about 20 to about 1
The two-layer structure according to (29), wherein the two-layer structure has a thickness of 00 nm and is deposited on the second main surface of the substrate and coated with a photosensitive material. (33) A multilayer structure, wherein the refractive index and the extinction coefficient in at least one layer of the thick lower anti-reflection layer continuously change from a low value to a higher value through the thickness of the layer. (34) a refractive index of about 1.8, an extinction coefficient of about 0.3,
The multilayer structure of claim 33, comprising at least one thick lower anti-reflective layer having a thickness of about 2 to about 30 nm. (35) a refractive index in the range of about 1.5 to 1.9 and about 0.1
An extinction coefficient in the range of 5 to 0.5 and about 100 to about 1000
(33) characterized in that it comprises at least one additional layer of a thick lower anti-reflection layer having a thickness of nm.
The multilayer structure according to 1. (36) characterized by having at least one additional layer of a thick lower anti-reflective layer having a refractive index of about 1.8, an extinction coefficient of about 0.21, and a thickness of about 100 to about 1000 °; The multilayer structure according to the above (33). (37) The multilayer structure according to the above (33), wherein the multilayer structure has at least one layer of a thick lower anti-reflection layer whose refractive index is smoothly graded from about 1.9 to about 1.5. . (38) The multilayer structure according to the above (33), wherein the multilayer structure has at least one layer of a thick lower anti-reflection layer that is smoothly graded from about 0.15 to about 0.5. (39) In a method of manufacturing an anti-reflection layer film adhered on a substrate, a step of providing a substrate on an electrode of a chamber for adhering the anti-reflection layer film, evacuating the chamber, Pre-cleaning the substrate and heating the substrate; introducing a gas forming the anti-reflective layer; and providing the chamber with a power density and / or time sufficient to deposit the anti-reflective layer. A method of manufacturing, comprising: exciting to form a coated substrate; and removing the coated substrate from the chamber. (40) The method according to (39), wherein the substrate is a semiconductor substrate. (41) The manufacturing method according to the above (39), wherein the chamber comprises a reactive sputtering chamber. (42) The method according to (39), wherein the step of evacuating the chamber includes evacuating the chamber to about 10 ⁻³ to about 10 ⁻⁷ Torr. (43) The step of heating the substrate is performed at about 25 ° C. to about 40 ° C.
The method according to (39), comprising heating the substrate to a temperature of 0 ° C. (44) The step of pre-cleaning the substrate includes the step of:
The manufacturing method according to the above (39), which comprises performing F sputter cleaning. (45) The step of introducing a gas for forming the deposited thick lower anti-reflection layer is performed using hexafluorobenzene (HF).
B) The method according to the above (39), which comprises introducing a gas. (46) The step of introducing the HFB gas further includes introducing a hydrocarbon gas and adjusting a relative amount thereof.
The method according to (45), wherein the refractive index of the thick lower anti-reflection layer becomes smaller as the relative amount of HFB increases. (47) The method according to (45), further comprising, during the deposition, introducing a gas having a dopant level selected from the group consisting of hydrogen, oxygen, and a combination thereof into the chamber. Manufacturing method. (48) providing a substrate, depositing a thick lower anti-reflective layer on the substrate, spin-coating a silicon-containing photoresist on top,
Baking for 90 seconds, and exposing the resist to DUV through a photomask.
Post baking for 0 second, developing the photoresist to form a patterned resist structure, and using the patterned resist structure as an etching mask with oxygen and / or fluorine containing plasma to form the thick bottom reflection. Forming a 250 nm or less line having a high aspect ratio by reactive ion etching of the prevention layer. (49) The structure according to (1), wherein the substrate is selected from the group consisting of a magnetic head, an electronic chip, a circuit board, and a semiconductor device. (50) A structure having a surface having a patterned antireflection film. (51) The structure according to (2), wherein said energy-active material is responsive to energy selected from the group consisting of electromagnetic radiation, particle beams, and heat. (52) The structure according to (51), wherein the particle beam is an electron beam. (53) The structure according to (17), wherein the dopant is selected from the group consisting of oxygen, silicon, and a combination thereof. (54) The method according to the above (39), wherein the step of heating is performed by means selected from the group consisting of optical, resistive, and a combination thereof. (55) The antireflection layer film has a thickness of about 100 to about 10,000
wherein the total thickness of the lower anti-reflective layer film of about 300 nm is deposited at a rate of about 2 to about 200 nm / min.
The production method according to the above (39). (56) The structure according to (1), wherein the at least one deposited antireflection film has a predetermined refractive index profile, a predetermined absorption coefficient profile, and a predetermined thickness. . (57) The at least one deposited anti-reflection film is formed by plasma deposition, sputter deposition, ion beam deposition,
(1) characterized in that it is selected from the group consisting of films deposited by vapor deposition, and combinations thereof.
Structure described in. (58) The structure according to (1), wherein the at least one deposited antireflection film is finely optically adjusted. (59) The step of exciting the chamber is to deposit the antireflection layer by a process selected from the group consisting of plasma deposition, sputter deposition, ion beam deposition, vapor deposition, and combinations thereof. The production method according to the above (39). (60) The method according to (39), further comprising a step of introducing a dopant. (61) The method according to (39), wherein the anti-reflection layer film is adhered so as to have a controlled thickness, refractive index, and extinction coefficient. (62) The structure according to (1), wherein at least one of the refractive index and the extinction coefficient has a non-uniform profile.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a vapor deposition apparatus useful for practicing the present invention.

FIG. 2 is a diagram showing a definition of a swing ratio.

FIG. 3 is a diagram showing reflectance contours (contours of reflectance R ₂ ) as a function of n and k for a lower layer of 300 nm.

FIG. 4 shows k and SiO ₂ for a 300 nm lower layer
Reflectance contours as a function of the thickness of (contour of the reflectance R ₂₎ is a diagram showing a.

FIG. 5 shows reflectance contours (reflectance R ₂ contours) as a function of n and k for a lower layer of 500 nm.

FIG. 6 shows k and SiO ₂ for a 500 nm lower layer.
The thickness function reflectance contours of a diagram showing a (contour of the reflectance R _2).

7 is a diagram showing a reflectance contours (contour of the reflectance R ₂₎ as a function of n and k for the lower layer of 700 nm.

FIG. 8: k and SiO ₂ for 700 nm lower layer
The thickness function reflectance contours of a diagram showing a (contour of the reflectance R _2).

FIG. 9 shows reflectance contours (reflectance R ₂ ) as a function of n and k for an adjustable lower layer having a thickness of about 500 nm.

FIG. 10 is a schematic view showing the structure of a multilayer resist.

FIG. 11 shows the measured reflectance and calculated transmittance of a carbon layer about 500 nm thick as described in Example 4.

FIG. 12 is a diagram showing calculated values of n and k corresponding to FIG. 11;

FIG. 13 shows the measured reflectance and calculated transmittance of the approximately 1000 nm thick carbon layer described in Example 4.

FIG. 14 is a diagram showing calculated n and k values corresponding to FIG. 13;

FIG. 15 is a diagram showing a process flow of a two-layer resist system.

FIG. 16 is Table 1 showing optical characteristics of a sample according to the present invention.

FIG. 17 is a diagram showing a simulation of how the line width of a resist varies with exposure energy.

FIG. 18 shows the total reflectivity of the wafer as a function of oxide (layer # 1) thickness.

FIG. 19 shows the calculated resist linewidth as a function of oxide thickness, illustrating that linewidth is significantly affected by small variations in thickness.

FIG. 20 shows a thin film stack with resist on top of ARC layer # 1, oxide layer # 2, and silicon substrate.

FIG. 21 illustrates the reflectivity of a resist as a function of oxide thickness.

FIG. 22 shows a curve of line width versus oxide thickness.

[Explanation of symbols]

 Reference Signs List 8 PECVD deposition apparatus 10 Chamber 11 Throttle valve 12 Shower head 13 Match box 14 RF power 15 Substrate 16 Plate 17 Resistive heater 19 Cathode 20, 21, 22, 23, 24, 25, 26 Pipe 27 Dielectric spacer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Timothy Alan Brunner United States 06877 Ridgefield, Westmoreland Road, Connecticut 27 (72) Inventor Alessandro Caesar Carregari United States 10566 Yorktown Heights, Hanover Street 756, New York 756 ( 72) Inventor Alfred Grill U.S.A. 10605 White Plains Overlook Road, New York 85 (72) Inventor Christopher V. Journeys U.S.A. yoke Town Heights Willowway Street 2289

Claims (42)

[Claims] A structure comprising a substrate having at least one major surface and at least one deposited anti-reflective coating. 2. The method according to claim 1, wherein the substrate is a semiconductor, a polymer, a glass,
The structure of claim 1, wherein the structure is selected from the group consisting of metals and combinations thereof. 3. The structure according to claim 2, wherein said substrate is a semiconductor made of silicon. 4. The structure of claim 1, wherein said anti-reflective coating is a lower layer coated with a layer of energy active material. 5. The structure of claim 4, wherein said energy active material is a silicon-containing photoresist. 6. The structure of claim 4, wherein the interface between the energy active material and the lower layer has a reflectivity of less than about 0.001. 7. The structure of claim 4, wherein the swing ratio reduction is at least about 10 or more. 8. The energy-active material is selected from the group consisting of a composition sensitive to UV wavelengths, a composition sensitive to DUV wavelengths, a composition sensitive to UV and DUV wavelengths, and combinations thereof. The structure according to claim 4, wherein 9. The method according to claim 1, wherein a refractive index and an extinction coefficient of the antireflection film are different from a first interface between the antireflection film and the substrate.
A second layer between the antireflection film and the energy-active material;
5. The structure according to claim 4, wherein the refractive index and the extinction coefficient of the energy active material and the substrate are adjusted so as to substantially coincide with the interface of the substrate. 10. The antireflection coating is characterized in that thickness and optical non-uniformity are substantially uniform due to a continuously changing refractive index and a continuously changing extinction coefficient. A structure according to claim 9. 11. The structure of claim 9, wherein said refractive index is adjustable between about 1.4 and about 2.1 at wavelengths of 365, 248, and 193 nm. 12. The structure of claim 9, wherein said extinction coefficient is adjustable between about 0.1 and about 0.6 at wavelengths of 365, 248, and 193 nm. 13. The structure according to claim 1, wherein said antireflection film is made of a material containing carbon. 14. The vapor-deposited material is diamond-like carbon (DLC), fluorinated diamond-like carbon (FDLC), fluorine- and hydrogenated diamond-like carbon (FHDLC), nitrogen-added diamond-like carbon. (NDLC), fluorinated and hydrogenated amorphous carbon, fluorinated amorphous carbon, fluorinated tetrahedral carbon, nitrogen-added amorphous carbon, nitrogen and hydrogenated amorphous carbon, nitrogen-added tetrahedral carbon, and combinations thereof 14. The structure according to claim 13, wherein the structure is selected from the group consisting of mating. 15. The structure of claim 14, wherein said material comprises a dopant. 16. The structure of claim 15, wherein said dopant is selected from the group consisting of oxygen, silicon, and combinations thereof. 17. The anti-reflection coating comprises a single-layer film of uniform thickness, wherein the single-layer film has wavelengths of 365, 248, and 193 nm and ranges from about 1.4 to about 2.1. The structure of claim 15, having a refractive index and an extinction coefficient in the range of about 0.1 to about 0.6. 18. The structure of claim 13, wherein said material is patternable and removable by reactive ion etching with a gas comprising oxygen, fluorine, and combinations thereof. 19. The method of claim 1, wherein the at least one deposited anti-reflective coating has a predetermined refractive index profile, a predetermined extinction coefficient profile, and a predetermined thickness. Construction. 20. The structure of claim 19, wherein said index of refraction ranges from about 1.4 to about 2.1. 21. The structure according to claim 19, wherein said extinction coefficient ranges from about 0.1 to about 0.6. 22. The method according to claim 11, wherein the antireflection film has a thickness of about
20. The structure of claim 19, having a uniform thickness of about 5000 nm. 23. The structure according to claim 19, wherein at least one of the refractive index and the extinction coefficient has a non-uniform profile. 24. The at least one deposited anti-reflective coating is selected from the group consisting of films deposited by plasma deposition, sputter deposition, ion beam deposition, deposition, and combinations thereof. The structure of claim 1. 25. An index of refraction in the range of about 1.5 to 1.7, an extinction coefficient in the range of about 0.25 to 0.45, and about 300 to 7
A two-layer structure, wherein a first layer of a lower antireflective layer having a thickness of 00 nm is deposited on a first major surface of the substrate. 26. A second layer of a lower anti-reflective layer having a refractive index of about 1.8, an extinction coefficient of about 0.21, and a thickness of about 20 to about 100 nm, wherein 26. The two-layer structure according to claim 25, wherein the two-layer structure is attached on a main surface of the first member and coated with a photosensitive material. 27. The two layers of the lower anti-reflection layer,
DLC, FDLC, FHDLC, NDLC, fluorine and hydrogenated amorphous carbon, fluorine added amorphous carbon, fluorine added tetrahedral carbon, nitrogen added amorphous carbon, nitrogen and hydrogenated amorphous carbon, nitrogen added tetrahedral carbon, 27. The two-layer structure according to claim 26, comprising: and a combination thereof. 28. The two-layer structure of claim 27, wherein the material of the lower anti-reflective layer comprises a dopant selected from the group consisting of oxygen, silicon, or a combination thereof. 29. A multi-layer structure wherein the refractive index and the extinction coefficient in at least one layer of the thick lower anti-reflection layer vary continuously from a lower value to a higher value through the thickness of said layer. 30. A method of manufacturing an anti-reflective layer film deposited on a substrate, comprising: providing a substrate on an electrode of a chamber for depositing the anti-reflective layer film; and evacuating the chamber. Pre-cleaning the substrate and heating the substrate; introducing a gas for forming the anti-reflective layer film; and a power density and / or time sufficient to adhere the anti-reflective layer film. And a step of exciting the chamber to form a substrate having the antireflection layer film attached thereto, and removing the substrate from the chamber. 31. The method according to claim 30, wherein said substrate is a semiconductor substrate. 32. The step of exciting the chamber comprises depositing the anti-reflective coating by a process selected from the group consisting of plasma deposition, sputter deposition, ion beam deposition, vapor deposition, and combinations thereof. The method according to claim 30, characterized in that: 33. The method according to claim 30, wherein said chamber comprises a reactive sputtering chamber. 34. The method of claim 30, wherein evacuating the chamber comprises evacuating the chamber to about ^10-3 to about ^10-7 Torr. 35. The step of heating the substrate, the step of heating the substrate at a temperature of about
Heating the substrate to a temperature of about 400 ° C.
The method according to claim 30. 36. The method according to claim 30, wherein the step of pre-cleaning the substrate includes RF sputter cleaning of the substrate. 37. The method according to claim 30, wherein the step of introducing a gas for forming the lower antireflection layer includes a step of introducing a hexafluorobenzene (HFB) gas. 38. The step of introducing the HFB gas further includes the step of introducing a hydrocarbon gas and adjusting the relative amount thereof, wherein the refractive index in the antireflection layer becomes smaller as the relative amount of HFB increases. 38. The method according to claim 37, wherein: 39. The method of claim 26, wherein introducing the HFB gas further comprises introducing a gas having a dopant level selected from the group consisting of hydrogen, oxygen, and combinations thereof into the chamber. Claim 37
The production method described in 1. 40. The method according to claim 30, further comprising a step of introducing a dopant. 41. A step of providing a substrate; a step of depositing a thick lower anti-reflective layer on the substrate; a step of spin-coating a silicon-containing photoresist on top; and a step of baking the photoresist at 90 ° C. for 90 seconds. Exposing the photoresist to DUV through a photomask;
A step of post-baking the resist at 120 ° C. for 90 seconds; a step of developing the photoresist to form a patterned resist structure; and a step of forming an oxygen and / or fluorine-containing plasma using the patterned resist structure as an etching mask. so,
Reactive ion etching the thick lower anti-reflective layer to form a 250 nm or less line having a high aspect ratio. 42. A structure having a surface having a patterned antireflection film.