New Volatile Perfluorinated Amidine–Carboxylate Copper(II) Complexes as Promising Precursors in CVD and FEBID Methods

In the present study, we have synthesised and characterised newly copper(II) complexes with the general formula [Cu2(NH2(NH=)CC2F5)2(µ–O2CRF)4], where RF = CF3, C2F5, C3F7, C4F9. Infrared spectroscopy, mass spectrometry with electron ionisation (EI MS), and density-functional theory (DFT) calculations were used to confirm compounds’ composition and structure. The volatility of the compounds was studied using thermal analysis (TGA), EI MS mass spectrometry, variable temperature infrared spectroscopy (VT IR), and sublimation experiments. Research has revealed that these compounds are the source of metal carriers in the gas phase. The thermal decomposition mechanism over reduced pressure was proposed. TGA studies demonstrated that copper transfer to the gaseous phase occurs even at atmospheric pressure. Two selected complexes [Cu2(NH2(NH=)CC2F5)2(µ–O2CC2F5)4] and [Cu2(NH2(NH=)CC2F5)2(µ–O2CC3F7)4] were successful used as chemical vapour deposition precursors. Copper films were deposited with an evaporation temperature of 393 K and 453 K, respectively, and a decomposition temperature in the range of 573–633 K without the use of hydrogen. The microscopic observations made to investigate the interaction of the [Cu2(NH2(NH=)CC2F5)2(µ–O2CC2F5)4] with the electron beam showed that the ligands are completely lost under transmission electron microscopy analysis conditions (200 keV), and the final product is copper(II) fluoride. In contrast, the beam energy in scanning electron microscopy (20 keV) was insufficient to break all coordination bonds. It was shown that the Cu-O bond is more sensitive to the electron beam than the Cu-N bond.

On the other hand, copper nanostructures are used, for example, in electronics [11][12][13], plasmonics [14,15], catalysis [16][17][18], and as antibacterial agents [19,20]. These structures can be obtained by gas-assisted methods such as chemical vapour deposition (CVD) [21][22][23] and focused electron beam induced deposition (FEBID) [24][25][26]. CVD is a process where one or more volatile precursors are transported in the vapour carrier gas to the reactor chamber, where they decompose on a heated substrate and deposit a solid material [27]. In FEBID, the precursor is supplied without the use of carrier gas, then the adsorbed compound is dissociated in the focus of an electron beam provided by a scanning or transmission electron microscope (SEM/TEM) [28]. For the FEBID deposition of metals, CVD precursors are often tested. However, in addition to being sufficiently volatile, the compound must also decompose under the influence of an electron beam [29]. In copper FEBID, several complexes previously used as CVD precursors, such as [Cu(hfac)(VTMS)], 2.4. Synthesis of [Cu 2 (NH 2 (NH=)CC 2 F 5 )) 2 (µ-O 2 CR F ) 4 ]) ((1)-(4)) Synthesis was carried out using Schlenk glassware and a glove box in an argon atmosphere. [Cu 2 (µ-O 2 CR) 4 ] (0.5 mmol, R = CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 ) was placed in a round-bottomed flask, and 20 cm 3 of anhydrous acetonitrile was added, followed by the introduction of pentafluoropropylamidine (AMDH, 1 mmol). The resulting dark-blue solution was stirred for 24 h. After this time, the solvent was removed under reduced pressure (1.3 × 10 −3 -1.3 × 10 −4 mbar). The obtained compounds were green-blue solids, stable in air. Yields ranged between 66% and 83%. No crystals suitable for an X-ray structure determination were obtained.

Infrared Spectra Analysis
In the infrared spectra (Supplementary Materials, Figures S1-S4), characteristic bands for asymmetric stretching vibrations of the carboxylate group were found over the range of 1649-1675 cm −1 (Table 1, Figure 1). Moreover, the value for symmetric stretching vibration was observed over the range of 1411-1443 cm −1 . The calculated parameter ∆ν = ν asCOO − ν sCOO , which is used for proposing of carboxylate coordination mode, was 206 cm −1 for the compound [Cu 2 (AMDH) 2 (µ-O 2 CCF 3 ) 4 ] (1), which was close to the ∆ν (RCOONa) value for sodium trifluoroacetate (223 cm −1 ). This suggests the bridging coordination mode of the carboxylate ligand. A similar relationship ∆ν ∼ = ∆ν (RCOONa) occurred for the next compounds (2)-(4) and the formation of the carboxylate bridges was proposed.  Interestingly, the band characteristic for the stretching vibrations of the =NH group shifts towards lower values for compounds (1) and (3) with an odd number of carbon atoms in the carboxylate chain and higher values for compounds (2) and (4) with an even number of carbon atoms in the carboxylate chain. There is also a difference in the area of the stretching bonds of the =NH and NH2 groups ( Figure 1 and Supplementary Materials, Figures S1-S4). It seems that, for compounds (1) and (3), the amidine arrangement in the structure is different than for compounds (2) and (4).

DFT Calculations
To confirm the way of amidine coordination, we decided to optimise the geometry using computational chemistry methods. For the complex [Cu2(AMDH)2(µ-O2CCF3)4] (1), calculations were started for the two structures in which the amidine coordination occurred through the =NH group (Figure 2a  Bands characteristic of the amidine molecule were also observed in the spectrum: stretching vibration of the C=N bond (1703-1710 cm −1 ), stretching vibration of a =NH group (3009-3240 cm −1 ), deformation vibrations of the NH 2 amino group (1597-1608 cm −1 ), and stretching of N=C-N group (1502-1510 cm −1 ). The coordination shifts of the signals mentioned above (relative to the free ligand) were in the range of 39-46 cm −1 , 72-121 cm −1 , 4-15 cm −1 , and 52-60 cm −1 , respectively ( Table 1). The obtained results suggest the amidine coordination through the =NH group because the coordination shift for the vibrations of this group has the most significant value.
Interestingly, the band characteristic for the stretching vibrations of the =NH group shifts towards lower values for compounds (1) and (3) with an odd number of carbon atoms in the carboxylate chain and higher values for compounds (2) and (4) with an even number of carbon atoms in the carboxylate chain. There is also a difference in the area of the stretching bonds of the =NH and NH 2 groups (Figure 1 and Supplementary Materials, Figures S1-S4). It seems that, for compounds (1) and (3), the amidine arrangement in the structure is different than for compounds (2) and (4).

DFT Calculations
To confirm the way of amidine coordination, we decided to optimise the geometry using computational chemistry methods. For the complex [Cu 2 (AMDH) 2 (µ-O 2 CCF 3 ) 4 ] (1), calculations were started for the two structures in which the amidine coordination occurred through the =NH group (Figure 2a) or -NH 2 (Figure 2b). The calculations showed that the lower energy structure is that in which the amidine was bound via the = NH group ( Figure 2). Therefore, in the case of complex (2), calculations were made only for the molecule with an amidine coordinated by the =NH bond ( Figure 2c) owing to the size of the molecule, and thus the long computation time.  It should be noted that the calculated structures are asymmetric, there is a distortion of the coordinated carboxylate, and the Cu-O bonds are not equal ( Figure 2). There are also differences in the spatial arrangement of amidines. The optimised structures confirm the different arrangement of the amidines in the structure for the compound (1) and (2). One of the amidine groups H2N-C=NH is perpendicular to the copper atoms, while the other is parallel.
Infrared spectra ( Figure 3) were also calculated for the two alternative optimised structures to confirm the assigned bands in the experimental spectra of the complexes (Table 1). In the area of stretching bonds characteristic of the -NH2 and =NH groups for compound (1), in the case of amidine coordination by the =NH group (Figure 2a), a slight It should be noted that the calculated structures are asymmetric, there is a distortion of the coordinated carboxylate, and the Cu-O bonds are not equal ( Figure 2). There are also differences in the spatial arrangement of amidines. The optimised structures confirm the different arrangement of the amidines in the structure for the compound (1) and (2). One of the amidine groups H 2 N-C=NH is perpendicular to the copper atoms, while the other is parallel.
Infrared spectra ( Figure 3) were also calculated for the two alternative optimised structures to confirm the assigned bands in the experimental spectra of the complexes (Table 1). In the area of stretching bonds characteristic of the -NH 2 and =NH groups for compound (1), in the case of amidine coordination by the =NH group (Figure 2a), a slight shift only in the position of the asymmetric stretching band of the -NH 2 group vibrations in relation to the free ligand is calculated (3716 cm −1 , AMDH; 3722 cm −1 , 3700 cm −1 , complex (1)). On the other hand, the band characteristic for the stretching vibrations of the =NH group shifts towards lower values (3540 cm −1 → 3498 cm −1 , 3485 cm −1 ). In the case of compound (1) alternative structure (Figure 2b) in which the amidine was coordinated by the -NH 2 group, a significant shift of the NH 2 asymmetric stretching vibrations towards lower values was observed (3716 cm −1 → 3591 cm −1 ). Comparing the theoretical and experimental infrared spectra for complex (1), it was confirmed that the amidine coordination occurs through the =NH group, because, in the experimental spectra, no significant shift of the band characteristic for the -NH 2 group was detected (Table 1). in the theoretical spectrum for complex (1), there is a double set of bands for asymmetric and symmetric stretching vibrations of the NH2 group. However, in the case of (2), only for -NH2 symmetrical stretching vibrations, a double set of bands was observed. As a result, more bands in the region >3000 cm −1 were observed in the spectrum for complex (1) than for complex (2), and it was also visible in the experimental spectra.
In the case of the stretching vibrations characteristic for the C=N group, no coordination shift was observed in the theoretical spectra ( Figure 3). It should be noted that the νC=N bands overlap with the asymmetric stretching vibrations of the carboxylic groups. Because the theoretical spectra were calculated for molecules in the gas phase, the individual bands are better separated. In the solid-phase spectrum (Figure 1), one band with the shoulder was observed, making it difficult to distinguish individual vibrations. The theoretical spectra also confirmed the proposed assignment of bands characteristic for deformation vibrations of the -NH2 group and stretching vibrations of the N=C-N group (Section 3.1). The νasN=C-N shifts more towards higher values (1442 cm −1 → 1485 cm −1 ) than the δNH2 (1602 cm −1 → 1623 cm −1 ).
In conclusion, both the calculated energies and the band coordination shifts in the experimental and theoretical spectrum confirmed the coordination of the amidine by the =NH group.

Thermal Analysis
Thermal analysis was performed to examine the behavior of the complexes during heating under a nitrogen atmosphere and to determine the final decomposition temperature and the degradation product. Only for complex (1), two decomposition stages can be distinguished (Figure 4a). For the other compounds (2-4), the thermal decomposition consists of several overlapping steps particularly visible in the derivative Interestingly, in the theoretical spectra, a difference was also observed in the shift of the stretching =NH band for complex (1) and (2) as in the experimental spectra. In compound (2), this band shifts towards higher values (3540 cm −1 → 3563 cm −1 ). Moreover, in the theoretical spectrum for complex (1), there is a double set of bands for asymmetric and symmetric stretching vibrations of the NH 2 group. However, in the case of (2), only for -NH 2 symmetrical stretching vibrations, a double set of bands was observed. As a result, more bands in the region >3000 cm −1 were observed in the spectrum for complex (1) than for complex (2), and it was also visible in the experimental spectra.
In the case of the stretching vibrations characteristic for the C=N group, no coordination shift was observed in the theoretical spectra ( Figure 3). It should be noted that the νC=N bands overlap with the asymmetric stretching vibrations of the carboxylic groups. Because the theoretical spectra were calculated for molecules in the gas phase, the individ-ual bands are better separated. In the solid-phase spectrum (Figure 1), one band with the shoulder was observed, making it difficult to distinguish individual vibrations.
The theoretical spectra also confirmed the proposed assignment of bands characteristic for deformation vibrations of the -NH 2 group and stretching vibrations of the N=C-N group (Section 3.1). The ν as N=C-N shifts more towards higher values (1442 cm −1 → 1485 cm −1 ) than the δNH 2 (1602 cm −1 → 1623 cm −1 ).
In conclusion, both the calculated energies and the band coordination shifts in the experimental and theoretical spectrum confirmed the coordination of the amidine by the =NH group.

Thermal Analysis
Thermal analysis was performed to examine the behavior of the complexes during heating under a nitrogen atmosphere and to determine the final decomposition temperature and the degradation product. Only for complex (1), two decomposition stages can be distinguished (Figure 4a). For the other compounds ((2)-(4)), the thermal decomposition consists of several overlapping steps particularly visible in the derivative graph ( Figure 4b). This may be because, for complexes (2), (3), and (4), a small amount of residue was observed ( Table 2) after the thermal analysis, which means that the complex can be partially evaporated under atmospheric pressure. However, under these conditions, in addition to evaporation, compound decomposition also occurs.  (Table 2) after the thermal analysis, which means that the complex can be partially evaporated under atmospheric pressure. However, under these conditions, in addition to evaporation, compound decomposition also occurs. showing the complexity of the decomposition process; (c) transmission electron microscope (TEM) diffraction pattern for the residue from TGA of (2); (d) energy-dispersive X-ray spectroscopy (EDX) spectrum for the residue after TGA of (2).
To confirm the composition of the final product of thermal analysis, transmission electron microscope (TEM) was used owing to the small amount left in the crucible. TEM diffraction pattern and EDX spectra (Figure 4c,d) revealed that the decomposition product under the conditions of thermal analysis (atmospheric pressure, nitrogen atmosphere) is copper(I) oxide.  (2) showing the complexity of the decomposition process; (c) transmission electron microscope (TEM) diffraction pattern for the residue from TGA of (2); (d) energy-dispersive X-ray spectroscopy (EDX) spectrum for the residue after TGA of (2). To confirm the composition of the final product of thermal analysis, transmission electron microscope (TEM) was used owing to the small amount left in the crucible. TEM diffraction pattern and EDX spectra (Figure 4c,d) revealed that the decomposition product under the conditions of thermal analysis (atmospheric pressure, nitrogen atmosphere) is copper(I) oxide.
The temperature of the decomposition process onset changed over the range of 337-391 K, and the temperature of the final product formation varied from 551 K (3) to 586 K (1) ( Table 2). For comparison, in the case of complexes mentioned in the Introduction with amines [Cu 2 ( t BuNH 2 ) 2 (µ-O 2 CR F ) 4 ], these values were 318-396 K and 458-668 K, respectively. Interestingly, in the case of complexes with CF 3 and C 2 F 5 substituents, lower T i and T f temperatures were observed for the complexes with tert-butylamine in the axial position. However, for the C 3 F 7 and C 4 F 9 chains, lower temperatures were registered for the complexes with amidine [41].

Mass Spectra Analysis
Mass spectra (EI-MS) of the studied compounds were registered between 303 and 623 K and applied to determine the composition of the complex and identify metallated fragments. The benefit of this approach is that the compound is first evaporated and then exposed to electrons (70 eV).
For all compounds, the pseudomolecular ion of the [Cu 2 (AMDH) 2 (O 2 CR F ) 3 ] + formula, where R F = C n F 2n+1 , n = 1-4, formed by the detachment of one carboxylate ligand, was visible in EI MS spectra (Table 3 and Tables S1-S3). Pseudomolecular ions of this type were previously observed for [Cu 2 ( t BuNH 2 ) 2 (µ-O 2 CR F ) 4 ] complexes with tert-butylamine in the axial position [41]. For compounds (1) and (2), this ion is already present at low temperatures: 313 K (RI = 4%) and 327 K (RI = 8%), respectively. The [Cu 2 (AMDH) 2 (O 2 CR F ) 3 ] + ion reaches its highest intensity over the temperature range of 353-396 K with only 2% RI for compound (3) and 67% RI for compound (1). The low intensity of the pseudomolecular ion for compound (3) may result from its high sensitivity to the electron beam, which caused its rapid decomposition. This is also evidenced by the high intensity of the [Cu 2 F] + ion, which is the end product of the decomposition ( Figure  5) and for the compound (3) reached 97% RI at 550 K (Table S2)     It is also worth noting the formation of ions containing coordinated ligands that were formed as a result of amidine decomposition, for example, [Cu 2 (NH 2 )(AMD) 2 (O 2 CCF 3 )] + , [Cu(AMDH)(HN=C=NH)] + , and [Cu(AMD)(HCN)] + . This may indicate that the formed Cu-N bond is strong. Therefore, the bonds in the ligand molecule were broken, and the amidine/amidinate was not completely detached.
Interestingly, at low temperatures (313-371 K), copper(I) and copper(II) fragments containing only N-donor ligands are also formed, such as [Cu 2 (AMD) 3 [50]. However, there is also release of amidine as a decomposition factor. The presence of [CO 2 H] + is evidence of amidine deprotonation by carboxylate and the formation of carboxylic acid and amidinate.
[Cu 2 F] + fragment was also detected in MS EI spectra for all studied compounds. It reaches an intensity of 13 to 97% RI at high temperatures (505-550 K) ( Table 3 and Tables  S1-S3). In the case of compound (2), [Cu] + ion was also observed. The formation of this type of ions indicates that electrons can cause the decomposition of compounds into copper(I) fluoride or copper (vide infra). This is a desirable property for the potential precursors used in the FEBID method.

Variable Temperature Infrared Spectroscopy (VT IR)
To examine the composition of the gas phase formed during the heating of the complexes, variable temperature infrared spectroscopy was carried out. The measurement conditions are similar to the deposition parameters during the CVD experiments.
At higher temperatures, there are more differences in the way compounds are decomposed. Generally, compounds (1), (3), and (4) have more decomposition stages than complex (2).
In the case of compound (1) in the third step of decomposition (stage III), there are characteristic bands for the entire complex (1) molecules, Cu-AMD, HAMD, and the carboxylic acid, at the temperature range of 473-533 K. The fourth stage of decomposition (stage IV) occurs in the temperature range of 553-593 K. The gas-phase contained the following species: Cu-AMD, Cu2(O2CCF3)4, HAMD, CF3COOH [55], CF3CFO, CO2, and  Figures S5-S7). In the case of complex (2), in addition to the molecules mentioned above, signals, 1824 cm −1 (ν as COO) and 1440 cm −1 (ν s COO) bands were observed in the gas phase at 553 K, characteristic for carboxylic acid ( Figure 6) [51].
At higher temperatures, there are more differences in the way compounds are decomposed. Generally, compounds (1), (3), and (4) have more decomposition stages than complex (2).
In the case of compound (1) in the third step of decomposition (stage III), there are characteristic bands for the entire complex (1) molecules, Cu-AMD, HAMD, and the carboxylic acid, at the temperature range of 473-533 K. The fourth stage of decomposition (stage IV) occurs in the temperature range of 553-593 K. The gas-phase contained the following species: Cu-AMD, Cu 2 (O 2 CCF 3 ) 4 , HAMD, CF 3 COOH [55], CF 3 CFO, CO 2 , and CO. The next stage (stage V, 613-633 K) differs from the previous one by the lack of metal carriers. In the last tested temperature range (stage VI, 653-753 K) in the gas phase, HAMD, CF 3 COOH, CO 2 , and CO ( Figure S5) were detected.
Compared with compound (1), in the third stage of complex (3) decomposition (stage III, 473-493 K), an additional band (2272 cm −1 ) was observed in the VT IR spectra. This band is characteristic of a gaseous C 2 F 5 CN. [56] At 513 K (stage IV), the gas phase consists of the following species: complex (3), Cu-AMD, HAMD, C 3 F 7 COOH [57], C 2 F 5 CN, and CO 2 . In turn, in the temperature range of 533-553 K (stage V), in addition to the aforementioned degradation products, CO molecule was detected. In the next step of decomposition (stage VI, 573-593 K), copper(II) perfluorobutyrate (1658 cm −1 ) was the only metal carrier. Additionally, the bands 1795 cm −1 (C=C stretching vibrations) and 1396 cm −1 (asymmetric C-F stretching mode in the CF 3 group) were recorded in the VT IR spectra characteristic of the CF 2 =CF-CF 3 molecule. [58] R F COOH, CF 3 CFO, C 2 F 5 CN, CO 2 , and CO were also observed in the gas phase at these temperatures. With increasing temperature (613-653 K, stage VI), the composition of the gas phase changes slightly compared with stage V, and there are no CF 3 CFO molecules ( Figure S6).
In the case of compound (4), the molecules Cu-AMD, HAMD, and C 4 F 9 COOH occur in the third phase of degradation (stage III, 493-533 K). In the next stage of decomposition (stage IV, 553-573 K), the gas phase is composed of Cu-AMD, HAMD, C 4 F 9 COOH [59], CF 3 CFO, C 2 F 5 CN, CO 2 , and CO. At higher temperatures (stage V, 593-613 K), the amount of gaseous products decreased, and Cu-AMD, HAMD, carboxylic acid, and CF 3 CFO were observed. Finally, in the last stage of decomposition (stage VI, 633-753 K), the gas phase consists only of CF 2 =CF-CF 3 and C 4 F 9 COOH ( Figure S7).
Based on the VT IR spectra and the ions observed in the gas phase during the EI MS experiments (Section 3.4), the thermal decomposition mechanism of compounds (1)-(4) was proposed, as shown in Figure 7. CO. The next stage (stage V, 613-633 K) differs from the previous one by the lack of metal carriers. In the last tested temperature range (stage VI, 653-753 K) in the gas phase, HAMD, CF3COOH, CO2, and CO ( Figure S5) were detected. Compared with compound (1), in the third stage of complex (3) decomposition (stage III, 473-493 K), an additional band (2272 cm −1 ) was observed in the VT IR spectra. This band is characteristic of a gaseous C2F5CN. [56] At 513 K (stage IV), the gas phase consists of the following species: complex (3), Cu-AMD, HAMD, C3F7COOH [57], C2F5CN, and CO2. In turn, in the temperature range of 533-553 K (stage V), in addition to the aforementioned degradation products, CO molecule was detected. In the next step of decomposition (stage VI, 573-593 K), copper(II) perfluorobutyrate (1658 cm −1 ) was the only metal carrier. Additionally, the bands 1795 cm −1 (C=C stretching vibrations) and 1396 cm −1 (asymmetric C-F stretching mode in the CF3 group) were recorded in the VT IR spectra characteristic of the CF2=CF-CF3 molecule. [58] RFCOOH, CF3CFO, C2F5CN, CO2, and CO were also observed in the gas phase at these temperatures. With increasing temperature (613-653 K, stage VI), the composition of the gas phase changes slightly compared with stage V, and there are no CF3CFO molecules ( Figure S6).
Based on the VT IR spectra and the ions observed in the gas phase during the EI MS experiments (Section 3.4), the thermal decomposition mechanism of compounds 1-4 was proposed, as shown in Figure 7. Based on the results described above, it can be concluded that complex (2) has the highest volatility. It was observed in the gas phase in the broadest temperature range. Moreover, the bands characteristic of this compound have a higher intensity than the bands assigned to degradation products in the temperature range of 433-533 K ( Figure   Figure 7. Proposed mechanism of [Cu 2 (AMDH) 2 (µ-O 2 CR F ) 4 ] thermal decomposition based on VT IR and EI MS studies. Based on the results described above, it can be concluded that complex (2) has the highest volatility. It was observed in the gas phase in the broadest temperature range. Moreover, the bands characteristic of this compound have a higher intensity than the bands assigned to degradation products in the temperature range of 433-533 K (Figure 8b). The inverse relationship was observed for compounds (1), (3), and (4) (Figure 8a,c,d). This means that complex (2) demonstrates the highest concentration in the gas phase. It is also worth adding that the concentration of other metal carriers is equally high. For this reason, this compound was selected as the best of the newly synthesised potential CVD precursors. Another compound ensuring a satisfactory amount of metal carriers in the gas phase was complex (3), which was also selected for testing in the CVD process. 8b). The inverse relationship was observed for compounds (1), (3), and (4) (Figure 8a,c,d). This means that complex (2) demonstrates the highest concentration in the gas phase. It is also worth adding that the concentration of other metal carriers is equally high. For this reason, this compound was selected as the best of the newly synthesised potential CVD precursors. Another compound ensuring a satisfactory amount of metal carriers in the gas phase was complex (3), which was also selected for testing in the CVD process.
Compared with the mass spectrometry results, no characteristic signals for carbodiimide or perfluorinated hydrocarbons (for compounds (1) and (2)) were detected in the VT IR spectra. It can be concluded that these products are formed only as a result of electron-induced decomposition rather than thermal decomposition. This observation confirms that VT IR spectra are an effective method for testing CVD precursors because the measurement conditions (10 −1 mbar) are close to those in the used CVD reactor.
It is also worth noting that relatively small changes in the compound structure (the carbon chain length increased in the carboxylate) affect the mechanism of compound decomposition. One interesting observation is the lack of a simple correlation between the carbon chain length in the carboxylate and complex volatility. Both complex (1) and complex (4) have a low concentration in the gas phase.
Compared with the mass spectrometry results, no characteristic signals for carbodiimide or perfluorinated hydrocarbons (for compounds (1) and (2)) were detected in the VT IR spectra. It can be concluded that these products are formed only as a result of electron-induced decomposition rather than thermal decomposition. This observation confirms that VT IR spectra are an effective method for testing CVD precursors because the measurement conditions (10 −1 mbar) are close to those in the used CVD reactor.

Sublimation Experiments
To further investigate the volatile species, sublimation experiments at 393 K and 1.3 × 10 −4 mbar were performed for compounds (1) and (2). Then, IR spectra were taken for the compounds deposited on the cooling finger. As can be seen for compound (2), the spectra before and after sublimation are similar (Figure 9 bottom). There are only slight differences in the positions and intensities of the bands assigned to the N-H stretching and deformation vibration. Therefore, it can be concluded that compound (2) evaporates without decomposition. In the case of compound (1), the changes in the IR spectra before and after sublimation are much more noticeable (Figure 9 top). It is worth mentioning that there are bands in the spectrum of the sublimation product characteristic for both coordinated ligands (3155 cm −1 , ν N-H ; 1724 cm −1 , ν C=N ; 1666 cm −1 , ν C=O ; 1543 cm −1 , δ NH ). This proves that compound (1) is a source of the metal carrier in the gas phase. It is likely that, during heating, a rearrangement in the structure of the compound occurs. The reason may be the breaking of hydrogen bonds between the molecules of the heated compound [60].

Sublimation Experiments
To further investigate the volatile species, sublimation experiments at 393 K and 1.3 × 10 −4 mbar were performed for compounds (1) and (2). Then, IR spectra were taken for the compounds deposited on the cooling finger. As can be seen for compound (2), the spectra before and after sublimation are similar (Figure 9 bottom). There are only slight differences in the positions and intensities of the bands assigned to the N-H stretching and deformation vibration. Therefore, it can be concluded that compound (2) evaporates without decomposition. In the case of compound (1), the changes in the IR spectra before and after sublimation are much more noticeable (Figure 9 top). It is worth mentioning that there are bands in the spectrum of the sublimation product characteristic for both coordinated ligands (3155 cm −1 , νN-H; 1724 cm −1 , νC=N; 1666 cm −1 , νC=O; 1543 cm −1 , δNH). This proves that compound (1) is a source of the metal carrier in the gas phase. It is likely that, during heating, a rearrangement in the structure of the compound occurs. The reason may be the breaking of hydrogen bonds between the molecules of the heated compound [60].

TEM and SEM Observations
To initially assess the sensitivity of compound (2) to the high-energy electron beam, observations were made using a scanning electron microscope (SEM, 20 keV) and a transmission electron microscope (TEM, 200 keV). Complex (2) was selected for testing because it demonstrates the best volatility. For SEM analysis, the compound was prepared by depositing its layer on a silicon wafer using the earlier described sublimation method (Section 3.6). For TEM analysis, the compound was dissolved in ethanol, and the resulting solution was applied to a mesh and allowed to solvent evaporate.
EDX spectra were taken during the SEM analysis, each of them recorded for 30 s. During the experiment, the scanning area was reduced, which increases the dose of

TEM and SEM Observations
To initially assess the sensitivity of compound (2) to the high-energy electron beam, observations were made using a scanning electron microscope (SEM, 20 keV) and a transmission electron microscope (TEM, 200 keV). Complex (2) was selected for testing because it demonstrates the best volatility. For SEM analysis, the compound was prepared by depositing its layer on a silicon wafer using the earlier described sublimation method (Section 3.6). For TEM analysis, the compound was dissolved in ethanol, and the resulting solution was applied to a mesh and allowed to solvent evaporate.
EDX spectra were taken during the SEM analysis, each of them recorded for 30 s. During the experiment, the scanning area was reduced, which increases the dose of electrons ( Figure 10). With the increasing dose of electrons, the oxygen content decreases, the carbon content is slightly reduced, and the copper content increases. The contents of the other elements were almost the same.  (Figure 10). With the increasing dose of electrons, the oxygen content decreases, the carbon content is slightly reduced, and the copper content increases. The contents of the other elements were almost the same. Based on the obtained results and the mass spectra (Section 3.4), the following mechanism of the compound decomposition under SEM conditions was proposed. In the first stage, a proton transfer from the amidine molecule to the carboxylate probably took place, resulting in the formation of a coordinated deprotonated amidine and C2F5COOH ( Figure 11). Ions with deprotonated amidine were observed in EI MS spectra (Table 3). Acid was decomposed by electrons, forming CO2 and C2F5H. This is confirmed by the EI MS spectra of the complexes (Section 3.4) and C2F5COOH [61], in which no molecular ion derived from the acid was observed. The unchanged amount of fluorine before compound interaction with electrons may indicate that C2F5H has not been released from the layer as a gas. Stoffels et al. proved by electron attachment mass spectrometry experiment that, in radio frequency fluorocarbon plasmas of CF4, C2F6, and C4F8, polymerisation occurred readily, and molecules containing up to ten carbon atoms have been found [62]. Therefore, it is possible that, during the interaction of C2F5H with the electron beam, polymerisation has occurred, and a carbon-fluorine matrix was formed.
In the second stage of decomposition, decarboxylation occurred, and the perfluorinated groups were still bound to the central atom. Formation of [Cu(CF3)2] -ion, with fluorocarbon group bonded to the copper atom, has been proved by Rijs et al. in their research on the mechanism of decomposition of [Cu2(µ-O2CCF3)4] using mass spectrometry [63]. Moreover, in the electron collision experiments with [Cu2(µ-O2CC2F5)4], the [Cu(CF3)2] -ion was formed [64].
It is seen that, during the interaction of the electron beam with a solid-phase compound, the amount of energy under SEM conditions is insufficient to remove the coordinated ligands effectively. The obtained results showed that the Cu-O bond is the weakest in the complex. The proposed mechanism of compound decomposition under the influence of the SEM electron beam is presented in Figure 11. It still seems necessary Based on the obtained results and the mass spectra (Section 3.4), the following mechanism of the compound decomposition under SEM conditions was proposed. In the first stage, a proton transfer from the amidine molecule to the carboxylate probably took place, resulting in the formation of a coordinated deprotonated amidine and C 2 F 5 COOH ( Figure 11). Ions with deprotonated amidine were observed in EI MS spectra (Table 3). Acid was decomposed by electrons, forming CO 2 and C 2 F 5 H. This is confirmed by the EI MS spectra of the complexes (Section 3.4) and C 2 F 5 COOH [61], in which no molecular ion derived from the acid was observed. The unchanged amount of fluorine before compound interaction with electrons may indicate that C 2 F 5 H has not been released from the layer as a gas. Stoffels et al. proved by electron attachment mass spectrometry experiment that, in radio frequency fluorocarbon plasmas of CF 4 , C 2 F 6 , and C 4 F 8 , polymerisation occurred readily, and molecules containing up to ten carbon atoms have been found [62]. Therefore, it is possible that, during the interaction of C 2 F 5 H with the electron beam, polymerisation has occurred, and a carbon-fluorine matrix was formed. to conduct FEBID experiments because, in this method, the precursor is deposited from the gas phase and, as evidenced by the EI MS spectrum (Section 3.4), in which the precursor is in gaseous form and interact with low-energy electrons, it is possible to decompose it into copper(I) fluoride. During TEM imaging, structural changes of the sample were visible from the beginning of the measurement. After a few seconds, only the image of the sample was stabilised, and crystallites were observed (Figure 12). The obtained diffraction confirmed the crystallinity of the formed substance with diffraction rings matching the cubic CuF2. In the second stage of decomposition, decarboxylation occurred, and the perfluorinated groups were still bound to the central atom. Formation of [Cu(CF 3 ) 2 ] − ion, with fluorocarbon group bonded to the copper atom, has been proved by Rijs et al. in their research on the mechanism of decomposition of [Cu 2 (µ-O 2 CCF 3 ) 4 ] using mass spectrometry [63]. Moreover, in the electron collision experiments with [Cu 2 (µ-O 2 CC 2 F 5 ) 4 ], the [Cu(CF 3 ) 2 ] − ion was formed [64].
It is seen that, during the interaction of the electron beam with a solid-phase compound, the amount of energy under SEM conditions is insufficient to remove the coordinated ligands effectively. The obtained results showed that the Cu-O bond is the weakest in the complex. The proposed mechanism of compound decomposition under the influence of the SEM electron beam is presented in Figure 11. It still seems necessary to conduct FEBID experiments because, in this method, the precursor is deposited from the gas phase and, as evidenced by the EI MS spectrum (Section 3.4), in which the precursor is in gaseous form and interact with low-energy electrons, it is possible to decompose it into copper(I) fluoride.
During TEM imaging, structural changes of the sample were visible from the beginning of the measurement. After a few seconds, only the image of the sample was stabilised, and crystallites were observed ( Figure 12). The obtained diffraction confirmed the crystallinity of the formed substance with diffraction rings matching the cubic CuF 2 .
in the complex. The proposed mechanism of compound decomposition under the influence of the SEM electron beam is presented in Figure 11. It still seems necessary to conduct FEBID experiments because, in this method, the precursor is deposited from the gas phase and, as evidenced by the EI MS spectrum (Section 3.4), in which the precursor is in gaseous form and interact with low-energy electrons, it is possible to decompose it into copper(I) fluoride. During TEM imaging, structural changes of the sample were visible from the beginning of the measurement. After a few seconds, only the image of the sample was stabilised, and crystallites were observed ( Figure 12). The obtained diffraction confirmed the crystallinity of the formed substance with diffraction rings matching the cubic CuF2. The EDX spectra of the TEM obtained material showed the following atomic contents of the elements: 11.6 at.% Cu, 41.2 at.% F, and 47.2 at.% C. Such values suggest that, apart from copper(II) fluoride formation, after the compound (2) interaction with the high-energy electron beam, a matrix consisting of fluorine and carbon is formed. However, it should be taken into account that the TEM grid was covered with carbon, which affects the semi-quantitative measurement. It is worth noting that the resulting material does not contain oxygen and nitrogen, which were in the pristine compound (2). This may indicate the breaking of Cu-N and Cu-O bonds under the conditions of TEM observation. The proposed mechanism of compound decomposition under the influence of the TEM electron beam is presented in Figure 13. The EDX spectra of the TEM obtained material showed the following atomic contents of the elements: 11.6 at.% Cu, 41.2 at.% F, and 47.2 at.% C. Such values suggest that, apart from copper(II) fluoride formation, after the compound (2) interaction with the high-energy electron beam, a matrix consisting of fluorine and carbon is formed. However, it should be taken into account that the TEM grid was covered with carbon, which affects the semiquantitative measurement. It is worth noting that the resulting material does not contain oxygen and nitrogen, which were in the pristine compound (2). This may indicate the breaking of Cu-N and Cu-O bonds under the conditions of TEM observation. The proposed mechanism of compound decomposition under the influence of the TEM electron beam is presented in Figure 13.
The microscopic observations showed that compound (2) is sensitive to the highenergy electron beam. It is visible that the decomposition of the compound strongly depends on the beam power and electron dose. When high electron energy (TEM) is used, CuF 2 is the final decomposition product, but in SEM, CO 2 detachment and organometallic species formation were suggested, while electrons have low energy (EI MS, Section 3.4), and Cu 2 F 2 is formed. The microscopic observations showed that compound (2) is sensitive to the highenergy electron beam. It is visible that the decomposition of the compound strongly depends on the beam power and electron dose. When high electron energy (TEM) is used, CuF2 is the final decomposition product, but in SEM, CO2 detachment and organometallic species formation were suggested, while electrons have low energy (EI MS, Section 3.4), and Cu2F2 is formed.

CVD Preliminary Experiments
Based on the volatility studies (TA, EI MS, VT IR-Sections 3.3-3.5), complexes (2) and (3) were selected for the hot-wall CVD experiments (Table 4). In the case of complex (2), the evaporation temperature of 393 K was sufficient to deposit the layer, while for precursor (3), it was necessary to increase the temperature to 453 K. This is consistent with the results of the VT IR analysis (Section 3.5), because for complex (2), the bands characteristic for the copper carriers appeared at lower temperatures (353 K) than for the complex (3) (433 K), and additionally they had higher intensities, which indicates a higher concentration of these metal carriers in the gas phase. The process was carried out using decomposition temperatures from 573 K to 633 K. The best results were obtained using 633 K as the deposition temperature TD.
The deposited layer was smooth (Figures 14b and 15b), and no impurity signals (C, N, O) were observed in the EDX spectrum (Figure 16a, red line). In the case of compound (2), nanometric layers with a thickness of 69-360 nm were produced ( Figure 14). It is seen that the higher evaporation temperature of the precursor results in a greater layer thickness (Figure 14a). This is consistent with the spectra of infrared spectroscopy because, at 393 K (Figure 8b), the concentration of the metal carriers in the gas phase was much lower than at 453 K (Figure 8b). Using the higher vaporization temperature (TV = 453 K) and lower deposition temperature (TD = 593 K) (Figure 14a), the grains (51-254 nm, Figure 15a) were more dispersed than at TV = 393 K and TD = 633 K (Figure 14b-d). The calculated roughness parameter Ra for the layer shown in Figure 14a was 51.0 nm, while for the films shown in Figure 14b-d, it was 11.1 nm, 11.1 nm, and 9.4 nm, respectively. This confirms that the layers deposited at lower vaporization and higher deposition temperature were smoother. The grain size for the films deposited at the higher temperatures was in the range of 36-201 nm (Figure 15c,d). Moreover, using a shorter

CVD Preliminary Experiments
Based on the volatility studies (TA, EI MS, VT IR-Sections 3.3-3.5), complexes (2) and (3) were selected for the hot-wall CVD experiments (Table 4). In the case of complex (2), the evaporation temperature of 393 K was sufficient to deposit the layer, while for precursor (3), it was necessary to increase the temperature to 453 K. This is consistent with the results of the VT IR analysis (Section 3.5), because for complex (2), the bands characteristic for the copper carriers appeared at lower temperatures (353 K) than for the complex (3) (433 K), and additionally they had higher intensities, which indicates a higher concentration of these metal carriers in the gas phase. The process was carried out using decomposition temperatures from 573 K to 633 K. The best results were obtained using 633 K as the deposition temperature T D . The deposited layer was smooth (Figures 14b and 15b), and no impurity signals (C, N, O) were observed in the EDX spectrum (Figure 16a, red line).
In the case of compound (2), nanometric layers with a thickness of 69-360 nm were produced ( Figure 14). It is seen that the higher evaporation temperature of the precursor results in a greater layer thickness (Figure 14a). This is consistent with the spectra of infrared spectroscopy because, at 393 K (Figure 8b), the concentration of the metal carriers in the gas phase was much lower than at 453 K (Figure 8b). Using the higher vaporization temperature (T V = 453 K) and lower deposition temperature (T D = 593 K) (Figure 14a), the grains (51-254 nm, Figure 15a) were more dispersed than at T V = 393 K and T D = 633 K (Figure 14b-d). The calculated roughness parameter R a for the layer shown in Figure 14a was 51.0 nm, while for the films shown in Figure 14b-d, it was 11.1 nm, 11.1 nm, and 9.4 nm, respectively. This confirms that the layers deposited at lower vaporization and higher deposition temperature were smoother. The grain size for the films deposited at the higher temperatures was in the range of 36-201 nm (Figure 15c,d). Moreover, using a shorter transport way of the metal carriers, densely packed single grains with a size of 138-445 nm were obtained (Figure 15b).
In the layer with a thickness of 69 nm deposited with complex (3), single, densely packed, round shape grains were also formed (Figure 17a). The continuity of the layer is also confirmed by the low value of the roughness parameter (R a = 9.9 nm). It is worth noting that using a higher evaporation temperature T V from 551 K (3) to 586 K for complex (3) leads to obtaining layers of similar thickness than when using a lower temperature for precursor (2). This also confirms the lower volatility of compound (3).
It is worth adding that both the precursor evaporation and decomposition temperatures were lower for the complex with perfluorinated amidine than for the previously used complex with t BuNH 2 [Cu 2 ( t BuNH 2 ) 2 (µ-O 2 CR f ) 4 ], which was 393 K, 453 K (amidine); 435-473 K ( t BuNH 2 ) and 573-633 K (amidine); 623-733 K ( t BuNH 2 ), respectively [42]. This shows that the introduction of a secondary perfluorinated ligand in the axial position increases the volatility of the compounds.
The EDX (SEM analysis) and XRD spectra of the layers showed that they contain metallic copper (Figure 16a,b and Figure 17b,c). The formation of metallic copper during the CVD process was also confirmed by the diffraction patterns and EDX spectra obtained by TEM analysis (Figures 16c and 17d,e). The great advantage of compound (2) is that it was possible to obtain pure copper films from the air-stable copper(II) complex in an argon atmosphere without using an additional reducing agent. However, in the case of complex (3), apart from metallic copper, copper(I) oxide and a small amount of carbon (2.9 at.%) were also detected. In contrast, the layers deposited with the use of [Cu 2 (NH 2 t Bu) 2 (µ-O 2 CR F ) 4 ] precursors contained metallic copper and a low content of fluorine (1.5 at.%) [42]. Interestingly, despite the high content of fluorine in compounds (2) and (3), it is not present in the obtained deposits.  In the layer with a thickness of 69 nm deposited with complex (3), single, densely packed, round shape grains were also formed (Figure 17a). The continuity of the layer is also confirmed by the low value of the roughness parameter (Ra = 9.9 nm). It is worth noting that using a higher evaporation temperature TV from 551 K (3) to 586 K for complex (3) leads to obtaining layers of similar thickness than when using a lower temperature for The EDX (SEM analysis) and XRD spectra of the layers showed that they contain metallic copper (Figures 16a,b and 17b,c). The formation of metallic copper during the CVD process was also confirmed by the diffraction patterns and EDX spectra obtained by TEM analysis (Figures 16c and 17d,e). The great advantage of compound (2) is that it was possible to obtain pure copper films from the air-stable copper(II) complex in an argon atmosphere without using an additional reducing agent. However, in the case of complex (3), apart from metallic copper, copper(I) oxide and a small amount of carbon (2.9 at.%) were also detected. In contrast, the layers deposited with the use of [Cu2(NH2 t Bu)2(µ-O2CRF)4] precursors contained metallic copper and a low content of fluorine (1.5 at.%) [42]. Interestingly, despite the high content of fluorine in compounds (2) and (3), it is not present in the obtained deposits.

Conclusions
Copper(II) carboxylate compounds with perfluorinated amidine of the general formula [Cu2(AMDH)2(µ-O2CRF)4], where RF = CF3, C2F5, C3F7, C4F9, were obtained by the reaction of copper(II) perfluorinated carboxylates with perfluorinated amidine. The IR spectra analysis suggested the bridging coordination mode of carboxylates. =NH-bonding of amidine was proposed from infrared spectra analysis and confirmed by DFT calculations. The structure of the obtained compounds was also confirmed by the results of the EI MS analysis. The following pseudomolecular ions [Cu2(AMDH)2(µ-O2CRF)3] + proved the dimeric structure of the studied complexes with bridging carboxylates forming the "paddle-wheel" structure and axially N-coordinated amidines. The results of mass spectrometry (MS-EI) and variable temperature infrared spectroscopy demonstrated that the synthesised compounds are a source of copper carriers in the gas phase. Studies have shown that the decomposition process of the compounds is complicated. However, two main mechanisms can be distinguished: amidine deprotonation and formation of volatile copper amidinates and a carboxylic acid, and amidine detachment followed by decarboxylation of copper carboxylate. Moreover, the thermal analysis showed that copper transfer to the gaseous phase occurred even at atmospheric pressure.
The preliminary CVD experiments confirmed that compounds (2) and (3) are the source of metal carriers in the gas phase. Complex (2) was also shown to be the most volatile. Copper films were successfully deposited using precursor (2) [Cu2(AMDH)2(µ-O2CC2F5)4] by the CVD method in the Ar atmosphere. The great advantage of the [Cu2(AMDH)2(µ-O2CC2F5)4] (2) is that a metallic film can be obtained from the air-stable copper(II) compound without the need to use any additional reducing agent such as H2.

Conclusions
Copper(II) carboxylate compounds with perfluorinated amidine of the general formula [Cu 2 (AMDH) 2 (µ-O 2 CR F ) 4 ], where R F = CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , were obtained by the reaction of copper(II) perfluorinated carboxylates with perfluorinated amidine. The IR spectra analysis suggested the bridging coordination mode of carboxylates. =NH-bonding of amidine was proposed from infrared spectra analysis and confirmed by DFT calculations. The structure of the obtained compounds was also confirmed by the results of the EI MS analysis. The following pseudomolecular ions [Cu 2 (AMDH) 2 (µ-O 2 CR F ) 3 ] + proved the dimeric structure of the studied complexes with bridging carboxylates forming the "paddlewheel" structure and axially N-coordinated amidines. The results of mass spectrometry (MS-EI) and variable temperature infrared spectroscopy demonstrated that the synthesised compounds are a source of copper carriers in the gas phase. Studies have shown that the decomposition process of the compounds is complicated. However, two main mechanisms can be distinguished: amidine deprotonation and formation of volatile copper amidinates and a carboxylic acid, and amidine detachment followed by decarboxylation of copper carboxylate. Moreover, the thermal analysis showed that copper transfer to the gaseous phase occurred even at atmospheric pressure.
The preliminary CVD experiments confirmed that compounds (2) and (3) are the source of metal carriers in the gas phase. Complex (2) was also shown to be the most volatile. Copper films were successfully deposited using precursor [Cu 2 (AMDH) 2 (µ-O 2 CC 2 F 5 ) 4 ] (2) by the CVD method in the Ar atmosphere. The great advantage of the [Cu 2 (AMDH) 2 (µ-O 2 CC 2 F 5 ) 4 ] (2) is that a metallic film can be obtained from the air-stable copper(II) compound without the need to use any additional reducing agent such as H 2 . The best results (smooth and pure structures) were achieved when the temperature of the precursor evaporation was 393 K, while the decomposition temperature was 633 K. Thanks to our research, we have obtained a promising compound that can be used as a precursor in CVD methods. Moreover, based on the study of the complexes' interactions with high-energy electrons, it can be concluded that the energy and dose influence the deposit composition and compound [Cu 2 (AMDH) 2 (µ-O 2 CC 2 F 5 ) 4 ] (2) may also be a precursor in the FEBID method for the preparation of nanostructures composed of copper(II) fluoride.

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Informed Consent Statement: Not applicable.

Data Availability Statement:
The data presented in this study are available on request from the corresponding author.