WO2020258390A1 - Film mince de phtalocyanine de métal composite à magnétisme réglable et son procédé de préparation - Google Patents

Film mince de phtalocyanine de métal composite à magnétisme réglable et son procédé de préparation Download PDF

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WO2020258390A1
WO2020258390A1 PCT/CN2019/095727 CN2019095727W WO2020258390A1 WO 2020258390 A1 WO2020258390 A1 WO 2020258390A1 CN 2019095727 W CN2019095727 W CN 2019095727W WO 2020258390 A1 WO2020258390 A1 WO 2020258390A1
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phthalocyanine
magnetic
evaporation
metal phthalocyanine
film
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PCT/CN2019/095727
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张宪民
阮刘霞
秦高梧
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东北大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/10—Magnetoresistive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Materials of the active region

Definitions

  • the invention belongs to the technical field of film preparation, and specifically relates to a magnetically adjustable composite metal phthalocyanine film and a preparation method thereof.
  • the phthalocyanine molecule has an 18-electron macrocyclic conjugated system, there is a strong ⁇ - ⁇ electron interaction, and it has a strong coordination ability. It can coordinate with almost all metal elements to form a metal complex with a special color It is commonly known as metal phthalocyanine.
  • Metal phthalocyanine compounds have good light stability, thermal stability and chemical stability, and show excellent optical, electrical, thermal, and magnetic properties and are used as molecular conductors, molecular electronic components, gas sensor devices, and molecules
  • the huge potential of new functional materials such as magnets, photoelectric conversion, electrochromic and liquid crystal displays, and their applications have expanded from the original dyes to various fields such as catalysis, solar energy, information technology, and medical and health.
  • the application of these high-tech metal phthalocyanines Aroused the great attention of scientists.
  • Metal phthalocyanines include transition metal phthalocyanines and rare earth metal phthalocyanines.
  • an organic co-evaporation method is used to co-evaporate a magnetic metal phthalocyanine and a non-magnetic metal phthalocyanine to prepare a composite metal phthalocyanine film.
  • the thickness of the film is between 10 and 100 nm, and the thickness ratio of the non-magnetic and magnetic metal phthalocyanine in the film is controlled by adjusting the evaporation temperature.
  • the magnetic properties of the composite metal phthalocyanine film can be continuously adjusted by changing the thickness ratio of the non-magnetic/magnetic metal phthalocyanine in the film.
  • a magnetically adjustable composite metal phthalocyanine film is composed of a magnetic metal phthalocyanine and a non-magnetic metal phthalocyanine.
  • the magnetic metal phthalocyanine is one of transition metal phthalocyanine or rare earth metal phthalocyanine
  • the non-magnetic metal phthalocyanine is one of transition metal phthalocyanines or rare earth metal phthalocyanines
  • the metal element in the composite metal phthalocyanine film with adjustable magnetic properties is one of 3d transition metal elements or lanthanides, wherein:
  • the 3d transition metal element is specifically Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn;
  • the lanthanide metal element is specifically La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
  • the magnetic metal phthalocyanine in the magnetically adjustable composite metal phthalocyanine film is chromium phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, gadolinium phthalocyanine, terbium phthalocyanine, dysprosium phthalocyanine, and holmium phthalocyanine , Erbium phthalocyanine, thulium phthalocyanine, and the rest are non-magnetic metal phthalocyanines.
  • the thickness of the magnetically adjustable composite metal phthalocyanine film is 10-100 nm.
  • the regulatable magnetic metal phthalocyanine composite films tested the saturation magnetization of the magnetic single magnetic phthalocyanine molecule is 3 ⁇ 12 ⁇ B, test temperature is 2K, an external magnetic field of 30kOe.
  • the method for preparing a composite metal phthalocyanine film with adjustable magnetic properties includes the following steps:
  • the substrate is a non-magnetic substrate such as platinum (111), gold (111), copper (111), carbon sixty, aluminum, or quartz glass.
  • the substrate temperature during the growth of the metal phthalocyanine film is set to room temperature.
  • the vacuum degree of the organic thermal evaporation equipment is less than 1.0 ⁇ 10 -5 Pa.
  • the evaporation time is 10-60 minutes, and the evaporation temperature is 360-480°C.
  • the evaporation temperature of the non-magnetic phthalocyanine is controlled so that the evaporation rate is between 0.02 and 0.1 angstroms/sec.
  • the thickness of the composite film obtained in 1h is 90nm.
  • the magnetic performance of the composite metal phthalocyanine film increases first and then decreases with the increase of the molar ratio of magnetic metal phthalocyanine/non-magnetic metal phthalocyanine.
  • Non-magnetic metal phthalocyanine does not only have a simple dilution effect, but It will have a complex magnetic interaction with the magnetic metal phthalocyanine. Therefore, organic semiconductor film materials with different magnetic properties can be obtained.
  • the 3d transition metals and the 3d and 4f electrons in the 4f rare earth elements selected in the present invention are all "protected" by the s or p electrons in the outer shell, so that most of their characteristics are still maintained during the atom bonding process.
  • the transition metal replaces the hydrogen in the phthalocyanine with a positive divalent state to form a planar metal phthalocyanine, and the rare earth element is coordinated with two phthalocyanine planes in a positive trivalent state to form a double-layer phthalocyanine structure.
  • the main function of the above-mentioned composite metal phthalocyanine film substrate is to support and improve film characteristics.
  • the surface of the substrate is required to have an ultra-high flatness.
  • the lattice matching of the film and the substrate is also a very important aspect. If the two lattices are not matched, a longer transition area will be formed in the early stage of film formation.
  • 3d transition metal elements Cr, Mn, Fe, Co corresponding divalent metal cation has a large magnetic moment, respectively 4.8 ⁇ B, 5.9 ⁇ B, 5.4 ⁇ B , 4.8 ⁇ B, which is mainly from the magnetic moment Contribution of electron spin.
  • the trivalent cations corresponding to Gd, Tb, Dy, Ho, Er, and Tm have larger magnetic moments, respectively 7.98 ⁇ B , 9.77 ⁇ B , 10.83 ⁇ B , 11.2 ⁇ B , 9.9 ⁇ B , 7.61 ⁇ B , these magnetic moments are contributed by the less than 4f electron layer.
  • the magnetic metal phthalocyanine mentioned above includes chromium phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, gadolinium phthalocyanine, terbium phthalocyanine, dysprosium phthalocyanine, holmium phthalocyanine, phthalocyanine Erbium, thulium phthalocyanine, and other metal phthalocyanines are non-magnetic metal phthalocyanines used to compound magnetic phthalocyanines.
  • composite phthalocyanine films with different thickness ratios are prepared by co-evaporation. Since the non-magnetic metal phthalocyanine is uniformly distributed in the magnetic metal phthalocyanine, the magnetic metal phthalocyanine molecules are effectively separated, thereby realizing effective control of the magnetic properties of the film. It provides an experimental basis for single-molecule magnets in various application device design and quantum computing.
  • Figure 1 is an XRD diffraction pattern of the composite metal phthalocyanine film (terbium phthalocyanine: lutetium phthalocyanine 1:2) prepared in Example 1;
  • Figure 2 is the M-H curve of the composite metal phthalocyanine film (terbium phthalocyanine: lutetium phthalocyanine 1:2) prepared in Example 1;
  • Figure 3 is an XRD diffraction pattern of the composite metal phthalocyanine film (iron phthalocyanine: copper phthalocyanine 4:1) prepared in Example 2;
  • Figure 4 is the M-H curve of the composite metal phthalocyanine film (iron phthalocyanine: copper phthalocyanine 4:1) prepared in Example 2;
  • Vacuum degree is 10 -6 Pa; 2. Heating temperature: 100-600°C; 3. Four evaporation sources, all equipped with baffles; 4. Film thickness control: film thickness probe 2 pcs, 2 film thickness gauges;
  • the substrate used is platinum (111), gold (111), copper (111), carbon sixty, aluminum or quartz glass substrate, among which:
  • Quartz glass substrate is purchased commercially, surface roughness (Ra) ⁇ 1.5nm, parallelism ⁇ 0.01mm;
  • the carbon sixty substrate is a 10nm thick C60 film prepared on a quartz glass substrate by thermal evaporation at 350°C and a vacuum degree of ⁇ 1.0 ⁇ 10 -5 Pa, with a growth rate of 0.13 angstroms/sec;
  • Metal substrates such as platinum (111), gold (111), copper (111), and aluminum are prepared by using magnetron sputtering equipment to prepare 10nm metal substrates on a quartz glass substrate: platinum (111), gold (111), Copper (111), aluminum; sputtering gas is Ar with purity ⁇ 99.999%, Ar gas flow rate is 30SCCM, ignition gas pressure is 1.0Pa, DC sputtering power is 10-60w, sputtering gas pressure is 4.0 ⁇ 10-1Pa, Annealing at 600°C for 1 hour, the corresponding platinum (111), gold (111), copper (111), and aluminum substrates were prepared;
  • the power of ultrasonic washing is 1200W and the frequency is 28KHz;
  • the magnetic test temperature for phthalocyanine molecules is 2K, and the external magnetic field is 30kOe.
  • the substrate is quartz glass.
  • Step 1 Put the powder samples of terbium phthalocyanine and lutetium phthalocyanine into two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Ultra-high vacuum organic thermal evaporation is used to prepare a metal phthalocyanine film composed of terbium phthalocyanine and lutetium phthalocyanine on glass, and the heating temperature of the two crucibles is adjusted. After adjusting the evaporation rate, open the substrate baffle and start organic evaporation coating. After 42 minutes of evaporation, a target thickness of 50nm terbium phthalocyanine: lutetium phthalocyanine composite film sample of 1:1 is obtained. When the evaporation temperature of terbium phthalocyanine is at 410°C, the evaporation rate becomes 0.1 angstroms/sec.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is Pt(111).
  • Step 1 Place the iron phthalocyanine and copper phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The Pt(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Pt(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare metal phthalocyanine film composed of iron phthalocyanine and copper phthalocyanine on Pt(111), adjust the heating temperature of the two crucibles to ensure that the evaporation rate of iron phthalocyanine and copper phthalocyanine is maintained Stable.
  • the evaporation temperature of phthalocyanine iron is 380°C
  • the evaporation rate becomes 0.2 angstroms/sec.
  • the target thickness of 100nm can be obtained after 67 minutes of evaporation.
  • the composite film sample of iron phthalocyanine: copper phthalocyanine is 4:1.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is C 60 .
  • Step 1 Place the dysprosium phthalocyanine and lanthanum phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The C 60 substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to dry the substrate with good ultrasound to ensure the cleanliness of the substrate surface.
  • Step 3 Place the substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of dysprosium phthalocyanine and lanthanum phthalocyanine on C 60 , adjust the heating temperature of the two crucibles to ensure that the evaporation rate of dysprosium phthalocyanine and lanthanum phthalocyanine remains stable.
  • the evaporation temperature of dysprosium phthalocyanine is at 408°C, the evaporation rate becomes 0.05 angstroms/sec, and the evaporation rate of lanthanum phthalocyanine is still 0.25 angstroms/sec at 426°C.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • Measured dysprosium phthalocyanine: phthalocyanine lanthanum single magnetic saturation magnetization phthalocyanine molecule 1:5 composite film is 12 ⁇ B, the composite film XRD pattern shown in Figure 5, MH curve shown in Figure 6.
  • the substrate is aluminum.
  • Step 1 Place the holmium phthalocyanine and lanthanum phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The aluminum substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in order, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the aluminum substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Use ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of holmium phthalocyanine and lanthanum phthalocyanine on an aluminum substrate. Adjust the heating temperature of the two crucibles to ensure that the evaporation rates of holmium phthalocyanine and lanthanum phthalocyanine are consistent When the evaporation temperature of holmium phthalocyanine is at 411°C, the evaporation rate is 0.1 angstroms/sec, and the evaporation rate of phthalocyanine holmium at 412°C is 0.1 angstroms/sec. After adjusting the evaporation rate, open the substrate baffle and start the organic evaporation coating.
  • a 1:1 thin film sample of holmium phthalocyanine:lanthanum phthalocyanine with a target thickness of 50 nm is obtained.
  • the evaporation temperature of holmium phthalocyanine is at 424°C, the evaporation rate becomes 0.2 angstroms/sec.
  • the evaporation rate of lanthanum phthalocyanine is still 0.1 angstroms/sec at 412°C, phthalocyanine with the target thickness of 50nm can be obtained after 23 minutes of evaporation.
  • the cyanine holmium: lanthanum phthalocyanine is a 2:1 thin film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Place the dysprosium phthalocyanine and lutetium phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10-5Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare metal phthalocyanine film composed of dysprosium phthalocyanine and lutetium phthalocyanine on glass, adjust the heating temperature of the two crucibles to ensure that the evaporation rates of dysprosium phthalocyanine and lutetium phthalocyanine remain consistent.
  • the evaporation rate of dysprosium cyanine at 408°C and lutetium phthalocyanine at 410°C are both 0.1 angstroms/sec. After adjusting the evaporation rate, open the substrate baffle and start organic evaporation coating. After 42 minutes of evaporation, a 1:1 thin film sample with a target thickness of 50 nm is obtained.
  • Dysprosium cyanine lutetium phthalocyanine is a 2:1 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Put the erbium phthalocyanine and lutetium phthalocyanine powder samples into two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10-5Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of erbium phthalocyanine and lutetium phthalocyanine on glass, adjust the heating temperature of the two crucibles to ensure that the evaporation rates of erbium phthalocyanine and lutetium phthalocyanine are consistent.
  • the evaporation temperature of cyanine erbium is 408°C and the evaporation temperature of lutetium phthalocyanine is 410°C
  • the evaporation rate is 0.1 angstroms/sec. After adjusting the evaporation rate, open the substrate baffle and start organic evaporation coating.
  • a 1:1 thin film sample of erbium phthalocyanine:lutetium phthalocyanine with a target thickness of 80 nm is obtained.
  • the evaporation temperature of phthalocyanine erbium is at 426°C, its evaporation rate becomes 0.25 angstroms/sec, ensuring that the evaporation rate of lutetium phthalocyanine is still 0.05 angstroms/sec at 405°C.
  • phthalocyanine with a target thickness of 80 nm can be obtained.
  • Cyanine: lutetium phthalocyanine is a 5:1 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is Cu(111).
  • Step 1 Place the cobalt phthalocyanine and copper phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The Cu(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Cu(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10-5Pa.
  • Step 4 Use ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of cobalt phthalocyanine and copper phthalocyanine on Cu(111), adjust the heating temperature of the two crucibles to ensure that the evaporation rate of cobalt phthalocyanine and copper phthalocyanine is maintained Stable.
  • the evaporation temperature of cobalt phthalocyanine is 380°C
  • the evaporation rate becomes 0.2 angstroms/sec.
  • the target thickness of 100nm can be obtained after 42 minutes of evaporation.
  • the cobalt phthalocyanine: copper phthalocyanine is a 1:1 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • Cobalt phthalocyanine measured: copper phthalocyanine saturation magnetization of a single magnetic molecules 1:1 phthalocyanine composite film was 6 ⁇ B.
  • the substrate is Cu(111).
  • Step 1 Place the chromium phthalocyanine and lanthanum phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The Cu(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Cu(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10-5Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of chromium phthalocyanine and lanthanum phthalocyanine on Cu(111), adjust the heating temperature of the two crucibles to ensure that the evaporation rate of the two types of metal phthalocyanine remains stable.
  • the evaporation temperature of chromium phthalocyanine is at 398°C, the evaporation rate becomes 0.45 angstroms/sec.
  • the evaporation rate of phthalocyanine lanthanum is still 0.05 angstroms/sec at 406°C, after 33 minutes of evaporation, 9 with the target thickness of 100 nm can be obtained. :1 Film sample.
  • phthalocyanine lanthanum is a 1:5 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Place the manganese phthalocyanine and cerium phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the glass substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of manganese phthalocyanine and cerium phthalocyanine on glass, adjust the heating temperature of the two crucibles to ensure that the evaporation rate of the two types of metal phthalocyanine remains stable.
  • the evaporation temperature of manganese is at 395°C
  • the evaporation rate becomes 0.4 angstroms/second, ensuring that the evaporation rate of cerium phthalocyanine is still 0.05 angstroms/second at 407°C.
  • an 8:1 film with a target thickness of 90nm can be obtained. sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Put the powder samples of gadolinium phthalocyanine and europium phthalocyanine into two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of gadolinium phthalocyanine and europium phthalocyanine, adjust the heating temperature of the two crucibles to ensure that the evaporation rate of gadolinium phthalocyanine and europium phthalocyanine remains stable.
  • the evaporation rate of gadolinium cyanine is 0.07 angstroms/sec when the evaporation temperature is 408°C
  • the evaporation rate of europium phthalocyanine is 0.01 angstroms/sec when the evaporation temperature is 410°C.
  • a 7:1 thin film sample of gadolinium phthalocyanine europium phthalocyanine with a target thickness of 80 nm is obtained.
  • the evaporation temperature of gadolinium phthalocyanine is at 427°C, the evaporation rate becomes 0.25 angstroms/sec.
  • the target thickness of 5 can be obtained at 80nm. :1 Film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Put the holmium phthalocyanine and praseodymium phthalocyanine powder samples into two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the glass substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of holmium phthalocyanine and praseodymium phthalocyanine on glass, adjust the heating temperature of the two crucibles to ensure that the evaporation rate of holmium phthalocyanine and lanthanum phthalocyanine remains the same.
  • the evaporation temperature of cyanine holmium is at 427°C
  • the evaporation rate is 0.3 angstroms/sec
  • the evaporation rate of phthalocyanine at 406°C is 0.05 angstroms/sec.
  • a film sample of holmium phthalocyanine:praseodymium phthalocyanine with a target thickness of 70 nm is obtained.
  • the evaporation temperature of holmium phthalocyanine is at 424°C, the evaporation rate becomes 0.2 angstroms/sec.
  • the evaporation rate of praseodymium phthalocyanine is still 0.1 angstroms/sec at 412°C, phthalocyanine with the target thickness of 50nm can be obtained after 23 minutes of evaporation.
  • the cyanine holmium: phthalocyanine praseodymium is a 2:1 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is quartz glass.
  • Step 1 Put the powder samples of thulium phthalocyanine and neodymium phthalocyanine into two evaporation crucibles at the same position.
  • Step 2 The glass substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the glass in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of thulium phthalocyanine and neodymium phthalocyanine on glass, adjust the heating temperature of the two crucibles to ensure that the evaporation rate of thulium phthalocyanine and neodymium phthalocyanine remains the same.
  • the evaporation rate of thulium cyanine is 0.5 angstroms/sec when the evaporation temperature is 447°C, and the evaporation rate of neodymium phthalocyanine is 0.1 angstroms/sec at 411°C.
  • neodymium phthalocyanine After adjusting the evaporation rate, open the substrate baffle and start the organic evaporation coating. After 11 minutes of evaporation, a 5:1 thin film sample of thulium phthalocyanine: neodymium phthalocyanine with a target thickness of 40 nm is obtained. When the evaporation temperature of thulium phthalocyanine is at 424°C, the evaporation rate becomes 0.2 angstroms/sec. When the evaporation rate of neodymium phthalocyanine is still 0.1 angstroms/sec at 411°C, after 22 minutes of evaporation, phthalocyanine with a target thickness of 40 nm can be obtained. Thulium cyanine: neodymium phthalocyanine is a 2:1 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the substrate is Pt(111).
  • Step 1 Place the cobalt phthalocyanine and zinc phthalocyanine powder samples in two evaporation crucibles at the same position.
  • Step 2 The Pt(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Pt(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Using ultra-high vacuum organic thermal evaporation to prepare a metal phthalocyanine film composed of cobalt phthalocyanine and zinc phthalocyanine on a Pt(111) substrate, adjust the heating temperature of the two crucibles to ensure the evaporation of cobalt phthalocyanine and zinc phthalocyanine The rate remains stable.
  • the evaporation temperature of cobalt phthalocyanine is at 376°C
  • the evaporation rate becomes 0.15 angstroms/sec.
  • the evaporation rate of zinc phthalocyanine is 0.05 angstroms/sec at 360°C, the target thickness can be obtained after 33 minutes of evaporation.
  • the 40nm cobalt phthalocyanine zinc phthalocyanine is a 3:1 film sample.
  • the evaporation rate becomes 0.05 angstroms/sec.
  • the target thickness of 40nm phthalocyanine can be obtained after 33 minutes of evaporation.
  • Cobalt cyanine zinc phthalocyanine is a 1:3 film sample.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • cobalt phthalocyanine: 1:3 zinc phthalocyanine can be achieved when a large magnetic moment of the thin film, a single magnetic saturation magnetization molecule phthalocyanine composite film was 7.5 ⁇ B.
  • the substrate is Cu(111).
  • Step 1 Put the powder samples of terbium phthalocyanine and scandium phthalocyanine into two evaporation crucibles at the same position.
  • Step 2 The Cu(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Cu(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10-5Pa.
  • Step 4 Ultra-high vacuum organic thermal evaporation is used to prepare a metal phthalocyanine film composed of terbium phthalocyanine and scandium phthalocyanine on a Cu(111) substrate, and the heating temperature of the two crucibles is adjusted.
  • the evaporation temperature of terbium phthalocyanine is at 410°C, the evaporation rate becomes 0.1 angstroms/sec, ensuring that the evaporation rate of scandium phthalocyanine is still 0.1 angstroms/sec at 361°C.
  • the evaporation temperature of terbium phthalocyanine is 410°C
  • the evaporation rate is 0.1 angstroms/sec
  • the evaporation rate of scandium phthalocyanine is still 0.2 angstroms/sec at 380°C
  • open the substrate baffle start organic evaporation coating, and evaporate
  • a target thickness of 20nm terbium phthalocyanine: scandium phthalocyanine 1:2 film sample can be obtained.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the film obtained a large magnetic moment a single magnetic saturation magnetization molecule phthalocyanine composite film was 10.2 ⁇ B.
  • the substrate is Pt(111).
  • Step 1 Put the terbium phthalocyanine and vanadium phthalocyanine powder samples into two evaporation crucibles at the same position.
  • Step 2 The Pt(111) substrate was ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and the ultrasonic time for each solvent was 20 minutes. Use nitrogen to blow dry the ultrasonically good substrate to ensure the cleanliness of the substrate surface.
  • Step 3 Place the Pt(111) substrate in the evaporation chamber of the ultra-high vacuum organic thermal evaporation equipment, and keep the vacuum degree of the evaporation chamber above 1.0 ⁇ 10 -5 Pa.
  • Step 4 Ultra-high vacuum organic thermal evaporation is used to prepare a metal phthalocyanine film composed of terbium phthalocyanine and scandium phthalocyanine on a Pt(111) substrate, and the heating temperature of the two crucibles is adjusted.
  • the evaporation temperature of terbium phthalocyanine is at 403°C, the evaporation rate becomes 0.05 angstroms/sec.
  • Step 5 Use the high-precision magnetic measurement instrument MPMS based on SQUID detection technology developed by Quantum Design of the United States to characterize the in-plane magnetic properties of the film.
  • the phthalocyanine Tb: 1:3 vanadium phthalocyanine can be achieved when a large magnetic moment of the thin film, a single magnetic saturation magnetization molecule phthalocyanine composite film was 10.5 ⁇ B.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)
  • Thin Magnetic Films (AREA)
  • Hall/Mr Elements (AREA)

Abstract

La présente invention concerne un film mince de phtalocyanine de métal composite à magnétisme réglable et son procédé de préparation. La phtalocyanine de métal comprend une phtalocyanine de métal de transition et une phtalocyanine de métal des terres rares. Le film mince de phtalocyanine de métal composite est la combinaison d'une phtalocyanine de métal magnétique et d'une phtalocyanine de métal non magnétique selon un rapport d'épaisseur de (9~1):(1~5). Un procédé de co-évaporation organique est appliqué à un substrat non magnétique de façon à co-évaporer la phtalocyanine de métal magnétique et la phtalocyanine de métal non magnétique pour préparer le film mince de phtalocyanine de métal composite. Le film mince présente une épaisseur de 10 à 100 nm, le rapport molaire entre la phtalocyanine de métal non magnétique et la phtalocyanine de métal magnétique est régulé en ajustant la température d'évaporation. Le magnétisme du film mince de phtalocyanine de métal composite peut être efficacement ajusté en modifiant le rapport molaire entre la phtalocyanine de métal non magnétique/magnétique, ce qui permet à la phtalocyanine de métal non magnétique d'être uniformément distribuée dans la phtalocyanine de métal magnétique de façon à séparer efficacement les molécules de phtalocyanine de métal magnétique.
PCT/CN2019/095727 2019-06-27 2019-07-12 Film mince de phtalocyanine de métal composite à magnétisme réglable et son procédé de préparation WO2020258390A1 (fr)

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CN113777137A (zh) * 2021-09-24 2021-12-10 昆明学院 一种基于铬酞菁单分子层薄膜的气体传感器及其制备方法和应用
CN113991019B (zh) * 2021-12-27 2022-03-11 天津大学 一种增强有机半导体薄膜形貌稳定性的方法

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