JPH02147385A - Information recording medium - Google Patents

Abstract

PURPOSE:To maintain a recorded information stably even under hot and humid conditions by providing a recording film comprising a Cu-Te alloy, carbon and hydrogen for recording information by irradiation with a laser light, on a substrate. CONSTITUTION:An information recording medium 18 comprises a substrate 13 and a recording film 14 provided thereon. The recording film 14, for recording information therein by irradiation with a laser light, comprises a Cu-Te alloy with a Cu content of 2-40atom%, carbon and hydrogen. With this construction, an information recording medium 18 can be provided which shows excellent oxidation resistance even in hot and humid environments and has a long useful life and high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention (Industrial Application Field) The present invention relates to an information recording medium on which information is recorded and reproduced by, for example, irradiation with laser light.

(Prior Art) As a type of information recording medium, information is recorded by irradiation with laser light and the recorded information is reproduced.
A device equipped with a recording film containing Te as a main component has been developed. Furthermore, a recording film containing carbon and hydrogen in addition to the Te-based recording film has been developed and put into practical use (see Japanese Patent Laid-Open No. 58-9234).

When creating this recording film, if Te is sputtered in an atmosphere containing hydrocarbon gas, the recording film (hereinafter referred to as Te
-C film) is obtained.

This recording film is an amorphous film made of Te, C and H.
It is known that at least C and H form a chemical bond.

This recording film cannot be formed even if it is attempted to be formed by vapor deposition using Te and hydrocarbon as sources (without using plasma) in the same way as the Te film, and can only be obtained by using plasma. This is because, after the hydrocarbon gas is once decomposed in the plasma, C and H undergo a half-chemical reaction to form a film, and this is a major feature when forming an optical recording film.

(Problems to be Solved by the Invention) When a recording film made of Te and hydrocarbons as described above is compared with a recording film made of Te at a high temperature and high humidity of 65° C. and 90% (accelerated conditions), Te The film oxidizes within just one week and optical recording performance is impaired, whereas Te-C
The membrane remained stable without being oxidized even after one month.

However, the recording film of the Te-C film also crystallizes at high temperatures (above about 75 degrees Celsius), resulting in a rough surface that increases noise and has a greater effect on the reproduced signal. .

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, it is an object of the present invention to provide an information recording medium that has a long life even in a high temperature and high humidity environment.

[Structure of the Invention] (Means for Solving the Problem) In order to achieve the above object, the present invention provides a substrate, a Cu-Te alloy formed on the substrate, and on which information is recorded by irradiation with a laser beam. and a recording film containing carbon and hydrogen.

Further, in the second invention, there is provided a substrate, a Cu film formed on the substrate, and on which information is recorded by irradiation with laser light.
The content of 'S is within the range of 2 at% to 40 at%
The present invention provides an information recording medium comprising an A'u-Te alloy and a recording film containing carbon and hydrogen.

By providing a recording film containing an alloy and carbon and hydrogen, recorded information can be stably maintained even under high temperature and high humidity conditions. Further, by controlling the content of -1u to X- within the range of 2 at % to 40 at %, a highly sensitive recording film can be obtained.

(Example) Hereinafter, one embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing the structure of an information recording medium 18 of the present invention. The information recording medium 18 of the present invention is composed of a substrate 13 and a recording film 14 laminated on the substrate 13.

The substrate 13 is made of a material that is transparent to the wavelength of laser light that is irradiated onto the information recording medium for recording and reproducing information. For example, when using a laser beam with an oscillation wavelength near infrared, polycarbonate (PC),
Polymethyl methacrylate (PMMA), glass, polyolefin, epoxy resin, etc. are used.

The recording film 14 is made of a Cu-Te alloy containing carbon and hydrogen.

The composition ratio of the Cu-Te alloy in this recording film 14 will be explained.

According to the already known phase diagram of the Cu-Te binary system,
As intermetallic compounds, Cu 2 Te, Cu 4 Te
3 and CuTe are known to exist. However, these compounds have melting points of 1125°C and 1125°C, respectively.
800°C and 600°C, and the melting point of the Te carrier (450°C
℃) is much higher.

Therefore, a heat mode recording method in which pits are formed by melting the recording film is not very practical.

However, the melting point of Cu27T e 73, which shows the eutectic point, is
The temperature is approximately 330°C, which is lower than that of Te. Therefore, the content ratio of Cu is preferably 2 to 40 atomic %. With this composition ratio, since the melting point is lower than that of To, recording can be performed with higher sensitivity than a Te film.

Further, if the thickness of the recording film 14 is 1000 angstroms or more, it is not preferable because the writing sensitivity decreases.

Therefore, the thickness must be 1000 angstroms or less, preferably 500 angstroms or less, and more preferably 100 to 300 angstroms. This has a pulse width of 60 n5e, as shown in Figure 2.
This is also clear from the writing sensitivity characteristics when the laser is incident through the substrate 13 under the condition of an es linear velocity of 5.5 m/see. If the film thickness is 350 angstroms or more and the writing laser power is low, the degree of modulation of the reproduced signal will not be obtained much, making it difficult to obtain excellent writing sensitivity characteristics. Also, 1
If the thickness is less than 0.00 angstroms, the recording film becomes discontinuous and the probability of pinhole formation increases, which is not preferable. In the case of heat mode recording, these pinholes may be mistaken for original pits during readout, and may also trigger oxidation of the recording film, so they must be minimized as much as possible.

Next, the tolerance of the reproduction laser power (the power level at which reproduction can be performed without causing deterioration of the recording film) of the information recording medium 18 shown in FIG. 1 will be explained. The reproducing laser light used to read out information recorded in the pits is normally continuously oscillated. In order to read out information with a good S/N ratio in this state, it is also necessary to increase the reproduction laser power.

However, if a certain threshold is exceeded, pits (information) may be destroyed and the level of reproduced reflected light may decrease. Therefore, the track was continuously held at a linear velocity of 5.5 s/see, the reproduction laser power was changed, and changes in the reflected light level were observed using a synchroscope. The observation results are shown in Figure 3.

According to this result, no matter the thickness of the recording film, 0.
With a laser power of 6 or 0.8 W, the level of reflected light did not change for 3 hours. However, when the power was increased to 11 vL, the level of reflection decreased within a few hours. In this case, the thinner the film, the greater the reduction in the reflection level.

The level of this reflected light is normalized with the level immediately after reproduction as 1.

The allowable playback power of the write-once recording film, which is currently being standardized, is a linear velocity of 5.5 m1sec at a rotational speed of 1800 rpm.
In this case, the maximum power is determined to be 0.5 mW. The maximum allowable reproduction laser power P++++ax (■W) is P
max fio, 2+〇, given by 055V. Here, V is the linear velocity (s/see) of the recording medium. Further, it is required that the level of reflected light does not change even after 10 cycles of continuous reproduction using P wax. This means that when the rotational speed is 180 rpm and the linear velocity is 5.5 layers/see, there should be no change for at least 1 hour. Therefore, the recording film 14 of the present invention has a 0.0.
Even with the power of 811IW, no change occurs for up to 3 hours, so this requirement is fully met.

Example 1 A method for forming the information recording medium 18 shown in FIG. 1 will be described.

FIG. 2 is a schematic diagram of a sputtering apparatus for forming the information recording medium 18. First, open the valve 2 of this sputtering device to the rotary pump 3 side and adjust the inside of the chamber 1 to 0.2To.
Exhausted to rr. Then valve 2 is connected to cryopump 5.
It was opened to the side and evacuated to below 1X10-'T Orr.

At this time, since there was no need to control the displacement, the conductance valve 4 was left fully open.

Next, the valve 6 was opened, and IO9CCM was introduced into the chamber 1 while adjusting Ar gas from the Ar gas line 7 using a mass flow controller (not shown). Next, while monitoring the pressure inside the chamber 1 with an ion gauge (not shown), the conductance valve 4
Adjusted to orr. After confirming that this pressure does not fluctuate, 100 W is applied from the DC power supply 10 to the Cu-Te alloy target 9 (diameter 5 inches; composition is Au 27 Te B; atomic %), and sputtering is performed with the shutter 11 closed. Spatter cleaning was performed by performing discharge for 5 minutes.

After stopping the supply of Ar gas and the supply of DC power, the inside of the chamber 1 is -HI
The exhaust was evacuated to below Torr. Then valves 6 and 1
7 and put Ar gas and CHa gas into chamber 1.
IO8C through r gas line 7 and CH4 gas line 8 while adjusting with a mass flow controller (not shown).
After introducing CM one by one, the pressure inside the chamber 1 was controlled to 5×10-'Torr using the conductance valve 4. After confirming that there is no pressure fluctuation, CuTe
100 W was applied to the target 9 from the DC power supply 10 to cause sputter discharge. After confirming that the discharge is stable, open the shutter 11 and close the rotor 12 in advance.
Polycarbonate (PC) board 1 set in
A recording film 14 containing a CuTe alloy and carbon and hydrogen was laminated on top of the recording film 14. The rotor was rotated at 60 rpm.

When the film thickness reached 250 angstroms, the shutter was closed and power supply was stopped.

Next, the conductance valve 4 was fully opened, and the inside of the chamber 1 was evacuated to 1×10 −' Torr or less using the cryopump 5. Next, the valve 15 was opened and N2 gas was introduced into the chamber 1 from the N2 gas line 16 to return the pressure to atmospheric pressure, and then the information recording medium 18 was taken out.

As a result of X-ray diffraction analysis, it was confirmed that the information recording medium 18 thus formed was an amorphous film in which no diffraction peak was observed from a specific diffraction angle. Unlike polycrystalline films, amorphous films do not have grain boundaries, so the reproduction laser light is not modulated at the grain boundaries and does not produce grain boundary noise.

Example 2 Information recording medium 1 manufactured by the method shown in Example 1
In No. 8, the ratio of read errors (error rate) occurring as a result of surface roughness due to oxidation, which is an index of oxidation resistance, was analyzed. A Te film and a Te-C film having the same thickness as that shown in Example 1 under accelerated conditions of 75° C.-90%,
Further, after each information recording medium provided with the recording film 14 of the present invention was left for a certain period of time, writing was performed and the error rate was measured. The measurement results are shown in FIG. The error rate was normalized with the value before being placed under acceleration conditions as 1.

According to the measurement results, the error rate of the Te film increases in just a few days. On the other hand, the recording film of the present invention showed almost no change even after being left for 1000 hours. Therefore, it can be seen that the recording film containing the CuTe alloy and carbon and hydrogen has good oxidation resistance even under high temperature and high humidity, and has a long life. The recording film of the present invention was found to be an amorphous film even when subjected to X-ray diffraction analysis after this measurement.

Figure 6 shows a pulse width of 50 n5ec and a writing frequency of 37
A GaAs semiconductor laser with a wavelength of 830 rv is used, and the numerical aperture (NA) of the objective lens is 0.52.
Linear velocity5. CZN when information is recorded on the Te-C film and the recording film of the present invention under the condition of 5 m/see.
It shows the size of the ratio (Carrier/Noise). This result also shows that in the recording film of the present invention,
It was found that the sensitivity was even higher than that of conventional recording films.

Example 3 Cu, Te in rare gas and hydrocarbon gas or hydrocarbon gas
When sputtering an alloy target, CuT in the recording film
The composition of the e-alloy may no longer be equal to the composition of the CuTe alloy target, resulting in an increase in Te in the recording film. Therefore, using the apparatus shown in FIG. 4, a film was formed under the same conditions as in Example 1 except that the composition of the CuTe alloy target was changed, and the composition of the CuTe alloy target and the carbon content in the recording film were
The compositional relationship of the uTe alloy was analyzed by ICP (Inductively Coupled Plasma Emission Spectroscopy) method. The results of this analysis are shown in FIG. It can be seen that the AuTe composition of the recording film 14 tends to contain 10% more Te than the composition of the target. Therefore, in order to form a recording film with a composition at the eutectic point (Cu27Te6i), it is desirable to manufacture an information recording medium using a target with a composition around Cu27Te6i.

Example 4 When sputtering a CuTe alloy target using only hydrocarbon gas, there are the following two drawbacks.

1) Cu Te alloy target with 100% hydrocarbon gas
The recording film obtained by sputtering in the atmosphere has a small optical absorption coefficient (absorption rate). For this reason, in the case of a heat mode recording method in which information is recorded by forming pits using heat generated when laser light is absorbed, a decrease in recording sensitivity is observed.

2) During sputtering of a CuTe alloy target, carbon powder, which is considered to be a decomposition product of hydrocarbon gas, is noticeably non-adherent on the target surface, so if sputtering is performed continuously for a long time, there is a risk that the sputtering film formation rate will decrease.

Here, the flow rate of hydrocarbon gas is X1, the flow rate of rare gas is Y, and the gas flow rate ratio is defined as Q-(X/ (X0Y))×100%, and Q-30, 50, 60 and 100%. A recording film (thickness: 250 Å, composition: Cu2
□Writing sensitivity characteristics of Tey1) were investigated. The result is shown in FIG.

When detecting this sensitivity characteristic, the rotation speed was set to 1850 rpm, and the pulse width was set to 6' On5ee. From this detection result, it can be seen that in the case of Q-100%, the laser power required to obtain a constant reproduced signal amplitude deteriorates the writing sensitivity significantly compared to other Q values. Furthermore, regarding the state of the target surface under each Q value, in the case of Q-100%, the target surface turned black the most and had more deposits. As the Q value decreased, the percentage of deposits tended to decrease. FIG. 9 shows the results of measuring error rates under the same acceleration conditions as in FIG. 5 for recording films formed under various Q values under the same conditions as in FIG. 8. Therefore, it can be seen from the results of FIGS. 8 and 9 that the sputtering condition Q is preferably 5≦Q≦50%.

Example 4 FIG. 10 shows the effect of the gas flow rate ratio Q on the sputtering rate. When sputtering is continued under conditions exceeding Q-50% (methane gas and argon gas, flow rate of methane gas is IO3CCM), the sputtering rate decreases. In FIGS. 10 and 11, the sputtering rate is normalized with the first value being 1. 1st
Figure 2 shows the flow rate of hydrocarbon gas (CM gas) at 10.20 and 11005C with the same flow rate ratio (Q-50%).
The sputtering rate when C is shown. As the flow rate increased, the amount of deposits on the target surface tended to increase. Therefore, it can be seen that the flow rate of hydrocarbon gas is preferably IO8CCM or less.

In this example, the CuTe target was sputter-discharged in a mixed atmosphere of hydrocarbon gas (methane) and rare gas (argon), but it may be discharged in an atmosphere of only hydrocarbon gas.

Further, in this embodiment, a transparent organic resin substrate is used, but the substrate may be opaque when the writing and reproducing laser beams are made incident from the recording film side without passing through the substrate.

[Effects of the Invention] As described above, according to the present invention, it is possible to provide an information recording medium having an optical recording film that exhibits excellent oxidation resistance even in a high temperature and high humidity environment, has a long life, and has high sensitivity.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an information recording medium according to an embodiment of the present invention, FIG. 2 is a diagram showing the relationship between recording film thickness and writing sensitivity, and FIG.
The figure shows changes in playback time and reflection level, Figure 4 shows a sputtering apparatus for manufacturing the information recording medium shown in Figure 1, and Figure 5 shows the error rate of the recording film under acceleration conditions. 6 is a diagram showing the results of comparing the recording sensitivities of the recording films. FIG. 7 is a diagram showing the relationship between the composition of the Cu Te alloy target and the composition of the Au Te alloy in the recording film.
The figure shows the relationship between writing laser power and modulation degree for each gas flow rate ratio, Figure 9 shows the relationship between acceleration time and error rate for each gas flow rate ratio, and Figure 10 shows the relationship between each gas flow rate ratio. FIG. 11 is a diagram showing changes in sputter rate for each hydrocarbon gas flow rate. 13... Substrate 14... Recording film 18... Information recording medium

Claims (2)

[Claims] (1) An information recording medium comprising: a substrate; and a recording film containing a Cu-Te alloy, carbon and hydrogen, formed on the substrate and on which information is recorded by irradiation with laser light. (2) A substrate, a Cu-Te alloy with a Cu content in the range of 2 atomic % to 40 atomic %, and elements and hydrogen formed on this substrate and on which information is recorded by irradiation with laser light. An information recording medium comprising: a recording film containing the following: