Broadly, the “film” that may appear floating on the water’s surface is likely a mix of lipids, proteins, algae, bacteria, particulate matter and microorganisms. Without a microscope, we can’t really identify exactly what the “film’s” composition is. It will vary from one aquarium to another. There is no definitive answer as to it’s cause and one hobbyists experience will be different from another, everything is purely anecdotal. In any case it is undesirable. It decelerates oxygen exchange, is unsightly and it’s microbiome is likely detrimental to aquaria health and stability.
I can not speak for surface skimmers that are seemingly popping up everywhere today, but I assume the popularity began when aquarists began replicating the ideaology of Takashi Amano. I am skeptical, to some degree, as these devices simply transfer the “film” from the surface of the water to filter media. The “film” may be out of sight, and oxygen levels improved, but it is still part of the water column. I am unaware of any legitimate studies done on these surface skimmers.
What I can tell you is I’ve easily removed surface “film” for years during water changes. I simply start a siphon with my python as usual, then angle the tube to the surface of the water. Creating a very thin layer of water, “skimming” into the tube creates a strong surface tension carrying all of the “film” down and out the tube. It may be difficult to picture this by reading text alone, but given a try you will figure out how this works. It will make a squeaking sort of flushing sound when done correctly. I do this during every water change and never have any “film” on top of any of my aquariums.
Hope this helps.